Polyacene derivatives and production thereof

ABSTRACT

The present invention relates to polyacene derivatives represented by general formula (I) below:  
                 
 
     (wherein R 1  to R 10 , etc. each represents hydrogen atom, hydrocarbon group, or an alkoxy group; A 1  and A 2  are hydrogen atom, a halogen atom, a hydrocarbon group, an alkoxy group, cyano group, etc.; n is an integer of not less than 1; R 6  and R 7  may be linked to each other to form a ring); and a process for preparing the polyacene derivatives from polyhydro compounds as well as electrically conductive materials comprising the polyacene derivatives. According to the process for preparing the polyacene derivatives of the present invention, optional substituents can be introduced into any carbon atoms of the polyacene, and the number of aromatic rings can be increased.

FIELD OF THE INVENTION

[0001] The present invention relates to polyacene derivatives and aprocess of producing the same.

BACKGROUND ART

[0002] It is known that conductive materials are obtained by dopingelectron donating molecules or electron accepting molecules intoconjugated polymers as organic conductive materials, includingpolyacetylene, polypyrrole, polyallylenevinylene,polythienylenevinylene, etc. It is also known that electron transfercomplexes formed by the combination of electron donating molecules suchas tetrathiafulvalene, bisethylenedithiotetrathiafulvalene, etc. andelectron accepting molecules such as tetracyanoquinodimethane,tetracyanoethylene, etc. exhibit a conductive property. Some of theseorganic conductive materials show high conductivity but can form a thinfilm only with difficulty. Furthermore, these conductive materialsinvolve a problem in terms of stability, since they are readily oxidizedin the air.

[0003] Since condensed polycyclic aromatic compounds like polyacenessuch as anthracene, naphthacene, pentacene, etc. are conjugatedpolymers, it is known that these compounds exhibit a conductive propertyby doping electron donating molecules or electron accepting moleculesinto these compounds. It has thus been expected to use these compoundsas electronic industry materials. Also, as the number of condensedbenzene rings in polyacenes increases, the band gap between HOMO andLUMO decreases theoretically so that it is expected to increase theconductive property of polyacenes. Therefore, even if the concentrationof dopants is low, it is likely to exhibit a sufficient conductiveproperty.

[0004] Condensed polycyclic aromatic compounds such as polyacenes,however, have a very poor solubility and are hardly soluble, when nosubstituent is introduced therein. For this reason, there is a limit tosynthesis methods using such condensed polycyclic aromatic compounds,and it was extremely difficult to process these compounds. It has thusbeen desired to introduce substituents on the side chains of condensedpolycyclic aromatic compounds to improve the solubility strikingly, andto produce polyacenes suitable for easy synthesis and processing. Inparticular, any process for synthesis of sequentially increasing thenumber of condensed benzene rings while introducing substituents thereinwas unknown.

[0005] Heretofore, a means for introducing optional substituents atoptional positions of polyacenes such as anthracene, naphthacene,pentacene, etc. has been limited to the Diels-Alder reaction.

[0006] For example, a process of producing decamethylanthracene isdescribed in Harold Hart, et al., “Decamethylanthracene and its10-‘Dewar’ Isomer,” Tetrahedron Letter, No.36, pp.3143-3146. Accordingto this process, the Diels-Alder reaction was applied to introducemethyl group into anthracene. Likewise in Tetrahedron, Vol. 43, No. 22,pp. 5403-5214, methyl group or the like was introduced into polyacenesby using the Diels-Alder reaction.

[0007] In the Diels-Alder reaction, there was a limit to substituentsthat can be introduced onto side chains. With respect to carbon atomsthat can be substituted onto side chains, their latitude was limited aswell. Further in the Diels-Alder reaction, it is impossible to increasethe number of condensed benzene rings sequentially. In the Diels-Alderreaction, it is necessary to design a scheme of synthesis, respectively,considering the individual structures of target compounds.

[0008] JPA Nos. H4-335087, H6-167807, H6-330032 and H10-36832 disclosesubstituted naphthacenes, and JPA No. H11-354277 discloses substitutedpentacenes. However, these compounds were all synthesized based onclassic methods of synthesis, and substituents that could be introducedor positions at which substituents could be introduced were limited. Andany process of synthesis for sequentially increasing the number ofcondensed benzene rings while introducing substituents was notdisclosed, either.

DISCLOSURE OF THE INVENTION

[0009] In one aspect of the present invention, it is an object tointroduce optional substituents into polyacenes at optional carbon atomsthereby to improve the solubility. By introducing substituents on theside chains of polyacenes, not only the solubility can be improved butfurther synthesis can be readily performed by introducing desiredsubstituents so that the side chains of the polyacenes can be modifiedin various ways. Thus, the number of condensed aromatic rings can beincreased sequentially while introducing substituents on the side chainsof polyacenes.

[0010] It is described in K. P. C. Vollhardt et al., Journal of AmericanChemical Society, 1985, 107, 5670 that 1,2-bis(trimethylsilyl)acetyleneis reacted with 1,2-diethynylbenzene in the presence of a catalyst suchas cyclopentadienylbiscarbonylcobalt, etc. to simultaneously form thetwo rings of 4-membered ring condensed to benzene and benzene ringcondensed to this 4-membered ring. That is, 3 rings are formed, takinginto account the benzene ring originally present. Since twotrimethylsilyl groups are present on the ortho-position on the 3ring-product, it is described that iodine chloride (ICl) is reacted withthe product followed by reacting with trimethylsilylacetylene underbasic conditions in the presence of palladium catalyst. There isdescribed such a scheme that the reaction is similarly repeated as suchto increase the number of condensed rings two at a time.

[0011] In one aspect of the present invention, there is provided apolyacene derivative represented by general formula (I) below:

[0012] (wherein:

[0013] each of R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹ and R¹⁰, which may bethe same or different, independently represents hydrogen atom; a C₁-C₄₀hydrocarbon group which may optionally be substituted; a C₁-C₄₀ alkoxygroup which may optionally be substituted; a C₆-C₄₀ aryloxy group whichmay optionally be substituted; an amino group which may optionally besubstituted; a hydroxy group; or a silyl group which may optionally besubstituted; provided that R⁶ and R⁷ may be cross-bridged with eachother to form a C₄-C₄₀ saturated or unsaturated ring, and the saturatedor unsaturated ring may be intervened by oxygen atom, sulfur atom or agroup shown by formula: —N(R¹¹)— (wherein R¹¹ is hydrogen atom or ahydrocarbon group), or may optionally be substituted;

[0014] each of A¹ and A², which may be the same or different,independently represents hydrogen atom; a halogen atom; a C₁-C₄₀hydrocarbon group which may optionally be substituted; a C₁-C₄₀ alkoxygroup which may optionally be substituted; a C₆-C₄₀ aryloxy group whichmay optionally be substituted; a C₇-C₄₀ alkylaryloxy group which mayoptionally be substituted; a C₂-C₄₀ alkoxycarbonyl group which mayoptionally be substituted; a C₇-C₄₀ aryloxycarbonyl group which mayoptionally be substituted; cyano group (—CN); carbamoyl group(—C(═O)NH₂); a haloformyl group (—C(═O)—X, wherein X represents ahalogen atom); formyl group (—C(═O)—H); isocyano group; isocyanategroup; thiocyanate group or thioisocyanate group; provided that A¹ andA² may be cross-bridged with each other to form a ring shown by formula:—C(═O)—B—C(═O)— (wherein B is oxygen atom or a group shown by formula—N(B¹)— (wherein B¹ is hydrogen atom, a C₁-C₄₀ hydrocarbon group or ahalogen atom));

[0015] n is an integer of not less than 1;

[0016] with proviso that, except for the case wherein R¹, R², R³, R⁴,R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, A¹ and A² are all hydrogen atoms;

[0017] when n is 1,

[0018] at least R¹, R², R⁴ and R⁹ are groups other than hydrogen atom,or at least R³, R⁵, R⁸ and R¹⁰ are groups other than hydrogen atom; and,

[0019] the cases of (a), (b), (c) and (d) below are excluded:

[0020] (a) when R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, A¹ and A² areall methyl groups;

[0021] (b) when R³, R⁴, R⁹ and R¹⁰ are all aryl groups that mayoptionally be substituted;

[0022] (c) when R¹, R², R⁴ and R⁹ are all alkoxy or aryloxy groups, andR³, R⁵, R⁶, R⁷, R⁸, R¹⁰, A¹ and A² are all hydrogen atoms;

[0023] (d) when R³, R⁵, R⁸ and R¹⁰ are all alkoxy or aryloxy groups, andR¹, R², R⁴, R⁶, R⁷, R⁹, A¹ and A² are all hydrogen atoms;

[0024] and, when n is 2, the cases of (a′), (b′), (c′) and (d′) beloware excluded:

[0025] (a′) a pentacene derivative represented by formula (Ia) below:

[0026] wherein R¹, R², R³, R⁴, R^(5a), R^(5b), R⁶, R⁷, R^(8a), R^(8b),R⁹, R¹⁰, A¹ and A² are all methyl groups; or R¹, R², R³, R⁴, R^(5a),R^(5b), R^(8a), R^(8b), R⁹ and R¹⁰ are all hydrogen atoms and at leastone of R⁶, R⁷, A¹ and A² is an aryl group; or at least one of R¹, R²,R³, R⁴, R^(5a), R^(5b), R⁶, R⁷, R^(8a), R^(8b), R⁹, R¹⁰, A¹ and A² is adiarylamine group;

[0027] (b′) a pentacene derivative represented by formula (Ib) below:

[0028] wherein R¹, R², R^(5b) and R^(8b) are all alkoxy or aryloxygroups;

[0029] (c′) a pentacene derivative represented by formula (Ic) below:

[0030] wherein at least 2 of R³, R^(5a), R^(8a) and R¹⁰ are aryl orarylalkynyl groups; or at least one of R³, R^(5a), R^(8a) and R¹⁰ is anarylalkenyl group; or R³, R^(5a), R^(8a) and R¹⁰ are all alkoxy oraryloxy groups;

[0031] (d′) a pentacene derivative represented by formula (Id) below:

[0032] wherein R⁴ and R⁹ are hydrogen atom, a hydrocarbon group, analkoxy group, an aryloxy group, a halogen atom or hydroxy group.)

[0033] In a further aspect of the present invention, preferably at least5 of R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, A¹ and A² are groups otherthan hydrogen atom, and more preferably at least 6 of R¹, R², R³, R⁴,R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, A¹ and A² are groups other than hydrogen atom.

[0034] The polyacene derivative described above is preferably apentacene derivative represented by formula (Ia):

[0035] (wherein:

[0036] each of R¹, R², R³, R⁴, R^(5a), R^(5b), R⁶, R⁷, R^(8a), R^(8b),R⁹ and R¹⁰, which may be the same or different, independently representshydrogen atom; a C₁-C₄₀ hydrocarbon group which may optionally besubstituted; a C₁-C₄₀ alkoxy group which may optionally be substituted;a C₆-C₄₀ aryloxy group which may optionally be substituted; an aminogroup which may optionally be substituted; a hydroxy group; or a silylgroup which may optionally be substituted; provided that R⁶ and R⁷ maybe cross-bridged with each other to form a C₄-C₄₀ saturated orunsaturated ring, and the saturated or unsaturated ring may beintervened by oxygen atom, sulfur atom or a group shown by formula:—N(R¹¹)— (wherein R¹¹ is hydrogen atom or a hydrocarbon group), or mayoptionally be substituted;

[0037] each of A¹ and A², which may be the same or different,independently represents hydrogen atom; a halogen atom; a C₁-C₄₀hydrocarbon group which may optionally be substituted; a C₁-C₄₀ alkoxygroup which may optionally be substituted; a C₆-C₄₀ aryloxy group whichmay optionally be substituted; a C₇-C₄₀ alkylaryloxy group which mayoptionally be substituted; a C₂-C₄₀ alkoxycarbonyl group which mayoptionally be substituted; a C₇-C₄₀ aryloxycarbonyl group which mayoptionally be substituted; cyano group (—CN); carbamoyl group(—C(═O)NH₂); a haloformyl group (—C(═O)—X, wherein X represents ahalogen atom); formyl group (—C(═O)—H); isocyano group; isocyanategroup; thiocyanate group or thioisocyanate group; provided that A¹ andA² may be cross-bridged with each other to form a ring shown by formula:—C(═O)—B—C(═O)— (wherein B is oxygen atom or a group shown by formula—N(B¹)— (wherein B¹ is hydrogen atom, a C₁-C₄₀ hydrocarbon group or ahalogen atom)), and

[0038] at least 5 of R¹, R², R³, R⁴, R^(5a), R^(5b), R⁶, R⁷, R^(8a),R^(8b), R⁹, R¹⁰, A¹ and A² are groups other than hydrogen atom, morepreferably at least 6 of R¹, R², R³, R⁴, R^(5a), R^(5b), R⁶, R⁷, R^(8a),R^(8b), R⁹, R¹⁰, A¹ and A² are groups other than hydrogen atom, furthermore preferably at least 7 of R¹, R², R³, R⁴, R^(5a), R^(5b), R⁶, R⁷,R^(8a), R^(8b), R⁹, R¹⁰, A¹ and A² are groups other than hydrogen atom,much more preferably at least 8 of R¹, R², R³, R⁴, R^(5a), R^(5b), R⁶,R⁷, R^(8a), R^(8b), R⁹, R¹⁰, A¹ and A² are groups other than hydrogenatom, further much more preferably at least 9 of R¹, R², R³, R⁴, R^(5a),R^(5b), R⁶, R⁷, R^(8a), R^(8b), R⁹, R¹⁰, A¹ and A² are groups other thanhydrogen atom, and most preferably at least 10 of R¹, R², R³, R⁴,R^(5a), R^(5b), R⁶, R⁷, R^(8a), R^(8b), R⁹, R¹⁰, A¹ and A² are groupsother than hydrogen atom.

[0039] In one aspect of the present invention, any one of thecombinations of R¹ and R², R³ and R¹⁰, R⁴ and R⁹, R⁵ and R⁸, R⁶ and R⁷,and A¹ and A² are preferably the same substituents; in one aspect of thepresent invention wherein the polyacene derivative is the pentacenederivative represented by the formula (Ia) above, any one of thecombinations of R¹ and R², R³ and R¹⁰, R⁴ and R⁹, R^(5a) and R^(8a),R^(5b) and R^(8b), R⁶ and R⁷, and A¹ and A² are preferably the samesubstituents.

[0040] In one aspect of the present invention, any one of R¹, R², R³,R⁴, R⁵, R⁶, R⁷, R⁸, R⁹ and R¹⁰ is preferably a C₁-C₄₀ hydrocarbon groupwhich may optionally be substituted, a C₁-C₄₀ alkoxy group which mayoptionally be substituted, or a C₆-C₄₀ aryloxy group which mayoptionally be substituted; in one aspect of the present invention, whenthe polyacene derivative is the pentacene derivative represented by theformula (Ia) above, any one of R¹, R², R³, R⁴, R^(5a), R^(5b), R⁶, R⁷,R^(8a), R^(8b), R⁹ and R¹⁰ is preferably a C₁-C₄₀ hydrocarbon groupwhich may optionally be substituted, a C₁-C₄₀ alkoxy group which mayoptionally be substituted, or a C₆-C₄₀ aryloxy group which mayoptionally be substituted.

[0041] In one aspect of the present invention, when n is 1, A¹ and A²may be an alkoxycarbonyl group, and R¹, R², R⁴ and R⁹ may be an alkyl oraryl group; or when n is 1, A¹, A², R¹, R², R⁴ and R⁹ may be an alkyl oraryl group; or further when n is 1, A¹ and A² may be a halogen atom andR³, R⁵, R⁶, R⁷, R⁸ and R¹⁰ may be an alkyl or aryl group.

[0042] In one aspect of the present invention, when the polyacenederivative is the pentacene derivative represented by the formula (Ia)above, A¹ and A² may be an alkoxycarbonyl group and R¹, R², R⁴, R^(5b),R⁶, R⁷, R^(8b) and R⁹ may be an alkyl or aryl group; or when thepolyacene derivative is the pentacene derivative represented by theformula (Ia) above, A¹, A², R¹, R², R⁴, R^(5b), R⁶, R⁷, R^(8b) and R⁹may be an alkyl or aryl group; or, when the polyacene derivative is thepentacene derivative represented by the formula (Ia) above,A^(1 l and A) ² may be a halogen group and R³, R^(5a), R^(8a) and R¹⁰may be an alkyl or aryl group.

[0043] In another aspect of the present invention, there is provided aprocess of producing the polyacene derivative represented by formula (I)below:

[0044] (wherein:

[0045] each of R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹ and R¹⁰, which may bethe same or different, independently represents hydrogen atom; a C₁-C₄₀hydrocarbon group which may optionally be substituted; a C₁-C₄₀ alkoxygroup which may optionally be substituted; a C₆-C₄₀ aryloxy group whichmay optionally be substituted; an amino group which may optionally besubstituted; a hydroxy group; or a silyl group which may optionally besubstituted; provided that R⁶ and R⁷ may be cross-bridged with eachother to form a C₄-C₄₀ saturated or unsaturated ring, and the saturatedor unsaturated ring may be intervened by oxygen atom, sulfur atom or agroup shown by formula: —N(R¹¹)— (wherein R¹¹ is hydrogen atom or ahydrocarbon group), or may optionally be substituted;

[0046] each of A¹ and A², which may be the same or different,independently represents hydrogen atom; a halogen atom; a C₁-C₄₀hydrocarbon group which may optionally be substituted; a C₁-C₄₀ alkoxygroup which may optionally be substituted; a C₆-C₄₀ aryloxy group whichmay optionally be substituted; a C₇-C₄₀ alkylaryloxy group which mayoptionally be substituted; a C₂-C₄₀ alkoxycarbonyl group which mayoptionally be substituted; a C₇-C₄₀ aryloxycarbonyl group which mayoptionally be substituted; cyano group (—CN); carbamoyl group(—C(═O)NH₂); a haloformyl group (—C(═O)—X, wherein X represents ahalogen atom); formyl group (—C(═O)—H); isocyano group; isocyanategroup; thiocyanate group or thioisocyanate group; provided that A¹ andA² may be cross-bridged with each other to form a ring shown by formula:—C(═O)—B—C(═O)— (wherein B is oxygen atom or a group shown by formula—N(B¹)— (wherein B¹ is hydrogen atom, a C₁-C₄₀ hydrocarbon group or ahalogen atom)); and,

[0047] n is an integer of not less than 1),

[0048] which comprises aromatizing hydrocarbon condensed ringsrepresented by formula (II) below:

[0049] (wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, A¹, A² and nhave the same significance as defined above;

[0050] the bond shown by formula below represents a single bond or adouble bond;

[0051] provided that when the bond is a single bond, hydrogen atom isfurther bound directly to the carbon atoms which are directly bound toR⁵, R⁶, R⁷ and R⁸);

[0052] in the presence of a dehydrogenation reagent.

[0053] In one embodiment of the present invention, the dehydrogenationreagent is a combination of a lithium dopant and a lithium-removingreagent. It is preferred to add first the lithium dopant to thehydrocarbon condensed rings and then add the lithium-removing reagent.Preferably, the lithium dopant is an alkyl lithium and thelithium-removing reagent is an alkyl halide.

[0054] In another embodiment of the present invention, thedehydrogenation reagent described above is preferably a compoundrepresented by formula (III) given below:

[0055] (wherein each of X¹, X², X³ and X⁴, which may be the same ordifferent, independently represents a halogen atom or cyano group).

[0056] In another embodiment of the present invention, thedehydrogenation reagent described above preferably contains palladium.

[0057] It is also preferred that at least 5 of R¹, R², R³, R⁴, R⁵, R⁶,R⁷, R⁸, R⁹, R¹⁰, A¹ and A² are groups other than hydrogen atom, morepreferably, at least 6 of R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, A¹and A² are groups other than hydrogen atom.

[0058] It is also preferred that the polyacene derivative describedabove is the pentacene derivative shown by formula (Ia) below:

[0059] (wherein R¹, R², R³, R⁴, R^(5a), R^(5b), R⁶, R⁷, R^(8a), R^(8b),R⁹, R¹⁰, A¹ and A² have the same significance as defined above), and

[0060] at least 5 of R¹, R², R³, R⁴, R^(5a), R^(5b), R⁶, R⁷, R^(8a),R^(8b), R⁹, R¹⁰, A¹ and A² are groups other than hydrogen atom. Morepreferably, at least 6 of R¹, R², R³, R⁴,R^(5a), R^(5b), R⁶, R⁷, R^(8a),R^(8b), R⁹, R¹⁰, A¹ and A² are groups other than hydrogen atom; furthermore preferably, at least 7 of R¹, R², R³, R⁴, R⁵, R^(5b), R⁶, R⁷,R^(8a), R^(8b), R¹⁰, A¹ and A² are groups other than hydrogen atom; muchmore preferably, at least 8 of R¹, R², R³, R⁴, R^(5a), R^(5b), R⁶, R⁷,R^(8a), R^(8b), R⁹, R¹⁰, A¹ and A² are groups other than hydrogen atom;further much more preferably, at least 9 of R¹, R², R³, R⁴, R^(5a),R^(5b), R⁶, R⁷, R^(8a), R^(8b), R⁹, R¹⁰, A¹ and A² are groups other thanhydrogen atom; and most preferably, at least 10 of R¹, R², R³, R⁴,R^(5a), R^(5b), R⁶, R⁷, R^(8a), R^(8b), R⁹, R¹⁰, A¹ and A² are groupsother than hydrogen atom.

[0061] Or, any one of the combinations of R¹ and R², R³ and R¹⁰, R⁴ andR⁹, R⁵ and R⁸, R⁶ and R⁷, and A¹ and A² are preferably the samesubstituents; in another aspect of the present invention, when thepolyacene derivative is the pentacene derivative represented by theformula (Ia) above, either the sets of R¹ and R², R³ and R¹⁰, R⁴ and R⁹,R^(5a) and R^(8a), R^(5b) and R^(8b), R⁶ and R⁷, or the set of A¹ and A²are preferably the same substituents.

[0062] Or, any one of R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹ and R¹⁰ ispreferably a C₁-C₄₀ hydrocarbon group which may optionally besubstituted; a C₁-C₄₀ alkoxy group which may optionally be substituted;or a C₆-C₄₀ aryloxy group which may optionally be substituted; in oneaspect of the present invention, when the polyacene derivative is thepentacene derivative represented by the formula (Ia) above, any one ofR¹, R², R³, R⁴, R^(5a), R^(5b), R⁶, R⁷, R^(8a), R^(8b), R⁹ and R¹⁰ ispreferably a C₁-C₄₀ hydrocarbon group which may optionally besubstituted, a C₁-C₄₀ alkoxy group which may optionally be substituted,or a C₆-C₄₀ aryloxy group which may optionally be substituted.

[0063] In the formula (I) above, the case that R¹, R², R³, R⁴, R⁵, R⁶,R⁷, R⁸, R⁹, R¹⁰, A¹ and A² are all hydrogen atoms may be excluded.

[0064] In the formula (I) above, when n is 1, at least R¹, R², R⁴ and R⁹may be groups other than hydrogen atom, or at least R³, R⁵, R⁸ and R¹⁰may be groups other than hydrogen atom, and the cases of (a), (b), (c)and (d) below may be excluded.

[0065] (a) when R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, A¹ and A² areall methyl groups;

[0066] (b) when R³, R⁴, R⁹ and R¹⁰ are all aryl groups that mayoptionally be substituted;

[0067] (c) when R¹, R², R⁴ and R⁹ are all alkoxy or aryloxy groups, andR³, R⁵, R⁶, R⁷, R⁸, R¹⁰, A¹ and A² are all hydrogen atoms;

[0068] (d) when R³, R⁵, R⁸ and R¹⁰ are all alkoxy or aryloxy groups, andR¹, R², R⁴, R⁶, R⁷, R⁹, A¹ and A² are all hydrogen atoms.

[0069] When the polyacene derivative is the pentacene derivativerepresented by formula (Ia) above, the cases of (a′), (b′), (c′) and(d′) below may be excluded:

[0070] (a′) the pentacene derivative represented by formula (Ia) below:

[0071] wherein R¹, R², R³, R⁴, R^(5a), R^(5b), R⁶, R⁷, R^(8a), R^(8b),R⁹, R¹⁰, A¹ and A² are all methyl groups; or R¹, R², R³, R⁴, R^(5a),R^(5b), R^(8a), R^(8b), R⁹ and R¹⁰ are all hydrogen atoms and at leastone of R⁶, R⁷, A¹ and A² is an aryl group; or at least one of R¹, R²,R³, R⁴, R^(5a), R^(5b), R⁶, R⁷, R^(8a), R^(8b), R⁹, R¹⁰, A¹ and A² is adiarylamine group;

[0072] (b′) the pentacene derivative represented by formula (Ib) below:

[0073] wherein R¹, R², R^(5b) and R^(8b) are all alkoxy or aryloxygroups;

[0074] (c′) the pentacene derivative represented by formula (Ic) below:

[0075] wherein at least 2 of R³, R^(5a), R^(8a) and R¹⁰ are aryl orarylalkynyl groups; or at least one of R³, R^(5a), R^(8a) and R¹⁰ is anarylalkenyl group; or R³, R^(5a), R^(8a) and R¹⁰ are

[0076] (d′) the pentacene derivative represented by formula (Id) below:

[0077] wherein R⁴ and R⁹ are hydrogen atom, a hydrocarbon group, analkoxy group, an aryloxy group, a halogen atom or hydroxy group.

[0078] Further in one aspect of the present invention, when n is 1, A¹and A² may be an alkoxycarbonyl group, and R¹, R², R⁴ and R⁹ may be analkyl or aryl group; or when n is 1, A¹, A², R¹, R², R⁴ and R⁹ may be analkyl or aryl group; or further when n is 1, A¹ and A² may be a halogenatom and R³, R⁵, R⁶, R⁷, R⁸ and R¹⁰ may be an alkyl or aryl group.

[0079] Further in one aspect of the present invention, when thepolyacene derivative is the pentacene derivative represented by theformula (Ia) above, A¹ and A² may be an alkoxycarbonyl group and R¹, R²,R⁴, R^(5b), R⁶, R⁷, R^(8b) and R⁹ may be an alkyl or aryl group; or whenthe polyacene derivative is the pentacene derivative represented by theformula (Ia) above, A¹, A², R¹, R², R⁴, R^(5b), R⁶, R⁷, R^(8b) and R⁹may be an alkyl or aryl group; or, when the polyacene derivative is thepentacene derivative represented by the formula (Ia) above, A¹ and A²may be a halogen group and R³, R^(5a), R^(8a) and R¹⁰ may be an alkyl oraryl group.

[0080] In another aspect of the present invention, there are providedconductive materials including the polyacene derivatives described aboveor the polyacene derivatives obtained by the process described above.

[0081] In another aspect of the present invention, there are providedresin compositions comprising the polyacene derivative described aboveor the polyacene derivative obtained by any process described above, andother synthetic organic polymers.

BRIEF DESCRIPTION OF THE DRAWINGS

[0082]FIG. 1 illustrates an example of the synthesis scheme of polyacenederivatives in accordance with the present invention.

[0083]FIG. 2 illustrates an example of the synthesis scheme of polyacenederivatives in accordance with the present invention.

[0084]FIG. 3 shows an X-ray crystal structure analysis of dimethyl5,12-dihydro-1,4,6,11-tetrapropylnaphthacene-2,3-dicarboxylate.

[0085]FIG. 4 shows an X-ray crystal structure analysis of dimethyl1,4,6,11-tetrapropylnaphthacene-2,3-dicarboxylate.

[0086]FIG. 5 illustrates an example of the synthesis scheme of polyacenederivatives in accordance with the present invention.

[0087]FIG. 6 shows an X-ray crystal structure analysis of dimethyl1,4,6,8,9,10,11,13-octaethyl-5,14-dihydropentacene-2,3-dicarboxylate.

PREFERRED EMBODIMENTS OF THE INVENTION

[0088] In one aspect of the present invention, there are providedpolyacene derivatives represented by formula (I) described below:

[0089] (wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, n, A¹ and A²have the same significance as defined above).

[0090] In the specification, the C₁-C₄₀ hydrocarbon group may be asaturated or unsaturated acyclic group, or a saturated or unsaturatedcyclic group. Where the C₁-C₄₀ hydrocarbon group is acyclic, the groupmay be linear or branched. The C₁-C₄₀ hydrocarbon group includes aC₁-C₄₀ alkyl group, a C₂-C₄₀ alkenyl group, a C₂-C₄₀ alkynyl group, aC₃-C₄₀ allyl group, a C₄-C₄₀ alkyldienyl group, a C₄-C₄₀ polyenyl group,a C₆-C₁₈ aryl group, a C₆-C₄₀ alkylaryl group, a C₆-C₄₀ arylalkyl group,a C₄-C₄₀ cycloalkyl group, a C₄-C₄₀ cycloalkenyl group, and the like.

[0091] The C₁-C₄₀ alkyl group, C₂-C₄₀ alkenyl group, C₂-C₄₀ alkynylgroup, C₃-C₄₀ allyl group, C₄-C₄₀ alkyldienyl group and C₄-C₄₀ polyenylgroup are preferably a C₁-C₂₀ alkyl group, a C₂-C₂₀ alkenyl group, aC₂-C₂₀ alkynyl group, a C₃-C₂₀ allyl group, a C₄-C₂₀ alkyldienyl groupand a C₄-C₂₀ polyenyl group, respectively; and more preferably a C₁-C₁₀alkyl group, a C₂-C₁₀ alkenyl group, a C₂-C₁₀ alkynyl group, a C₃-C₁₀allyl group, a C₄-C₁₀ alkyldienyl group and a C₄-C₁₀ polyenyl group,respectively.

[0092] Examples of the alkyl group useful for practicing the presentinvention, which may optionally be substituted, are, but not limitedthereto, methyl, ethyl, propyl, n-butyl, t-butyl, dodecanyl,trifluoromethyl, perfluoro-n-butyl, 2,2,2-trifluoroethyl, benzyl,2-phenoxyethyl, etc.

[0093] Examples of the aryl group, which is useful for practicing thepresent invention, are, but not limited thereto, phenyl, 2-tolyl,3-tolyl, 4-tolyl, naphthyl, biphenyl, 4-phenoxyphenyl, 4-fluorophenyl,3-carbomethoxyphenyl, 4-carbomethoxyphenyl, etc.

[0094] Examples of the alkoxy group useful for practicing the presentinvention, which may optionally be substituted, are, but not limitedthereto, methoxy, ethoxy, 2-methoxyethoxy, t-butoxy, etc.

[0095] Examples of the aryloxy group useful for practicing the presentinvention, which may optionally be substituted, are, but not limitedthereto, phenoxy, naphthoxy, phenylphenoxy, 4-methylphenoxy, etc.

[0096] Examples of the amino group useful for practicing the presentinvention, which may optionally be substituted, are, but not limitedthereto, amino, dimethylamino, methylamino, methylphenylamino,phenylamino, etc.

[0097] The silyl group useful for practicing the present invention,which may optionally be substituted, includes groups shown by formula:—Si(R¹²)(R¹³)(R¹⁴) (wherein each of R², R¹³ and R¹⁴, which may be thesame or different, independently represents a C₁-C₄₀ alkyl group whichmay optionally be substituted with a halogen atom; a C₆-C₄₀ arylalkylgroup which may optionally be substituted with a halogen atom; a C₁-C₄₀alkoxy group which may optionally be substituted with a halogen atom; ora C₆-C₄₀ arylalkyloxy group which may optionally be substituted with ahalogen atom).

[0098] Examples of the silyl group useful for practicing the presentinvention, which may optionally be substituted, are, but not limitedthereto, trimethylsilyl, triethylsilyl, trimethoxysilyl, triethoxysilyl,diphenylmethylsilyl, triphenylsilyl, triphenoxysilyl,dimethylmethoxysilyl, dimethylphenoxysilyl, methylmethoxyphenyl, etc.

[0099] The C₁-C₄₀ hydrocarbon group, C₁-C₄₀ alkoxy group, C₆-C₄₀ aryloxygroup, amino group, silyl group, etc. may optimally be substituted, andthe substituents are, for example, a halogen atom, hydroxy group, aminogroup, etc.

[0100] Examples of the halogen atom include fluorine atom, chlorineatom, bromine atom and iodine atom. When the hydrogen atom(s) of theC₁-C₄₀ hydrocarbon group, C₁-C₄₀ alkoxy group, C₆-C₄₀ aryloxy group,etc. are substituted with fluorine atom(s), the solubility of thepolyacene derivatives increases, which is preferred.

[0101] R⁶ and R⁷ may be cross-bridged with each other to form a C₄-C₄₀saturated or unsaturated ring. The unsaturated ring may be an aromaticring such as a benzene ring, etc. The ring formed by linking R⁶ and R⁷together is preferably a 4-membered ring to a 16-membered ring, morepreferably a 4-membered ring to a 12-membered ring. The ring may be anaromatic ring or an aliphatic ring. The ring may optionally besubstituted with substituents such as a C₁-C₂₀ hydrocarbon group, aC₁-C₂₀ alkoxy group, a C₆-C₂₀ aryloxy group, an amino group, hydroxygroup, a silyl group, etc.

[0102] The saturated or unsaturated ring described above may beintervened by oxygen atom, sulfur atom or the group shown by formula—N(R¹¹)— (wherein R¹¹ is hydrogen atom or a hydrocarbon group).Preferably R¹¹ is hydrogen atom or a C₁-C₆ alkyl group, more preferablyhydrogen atom or a C₁-C₄ alkyl group.

[0103] Each of A¹ and A², which may be the same or different,independently represents hydrogen atom; a halogen atom; a C₁-C₄₀hydrocarbon group which may optionally be substituted; a C₁-C₄₀ alkoxygroup which may optionally be substituted; a C₆-C₄₀ aryloxy group whichmay optionally be substituted; a C₇-C₄₀ alkylaryloxy group which mayoptionally be substituted; a C₂-C₄₀ alkoxycarbonyl group which mayoptionally be substituted; a C₇-C₄₀ aryloxycarbonyl group which mayoptionally be substituted; cyano group (—CN); carbamoyl group(—C(═O)NH₂); a haloformyl group (—C(═O)—X, wherein X represents ahalogen atom); formyl group (—C(═O)—H); isocyano group; isocyanategroup; thiocyanate group or thioisocyanate group.

[0104] The cyano group (—CN); carbamoyl group (—C(═O)NH₂); haloformylgroup (—C(═O)—X, wherein X represents a halogen atom); formyl group(—C(═O)—H); isocyano group; isocyanate group; thiocyanate group orthioisocyanate group can be converted from, e.g., an alkoxycarbonyl, ina conventional manner of the organic chemistry. The carbamoyl group(—C(═O)NH₂), haloformyl group (—C(═O)—X, wherein X represents a halogenatom), formyl group (—C(═O)—H) or the like can be converted into cyanogroup or the alkoxycarbonyl group, and vice versa.

[0105] A¹ and A² may be cross-bridged with each other to form a ringshown by formula: —C(═O)—B—C(═O)— (wherein B is oxygen atom or a groupshown by formula —N(B¹)— (wherein B¹ is hydrogen atom, a C₁-C₄₀hydrocarbon group or a halogen atom). For example, when A¹ and A² arealkoxycarbonyl groups, the groups can be converted into the carboxygroups in a conventional manner of the organic chemistry, and theadjacent carboxyl groups can be dehydrated and thus converted into thecarboxylic anhydride, namely, a ring shown by formula: —C(═O)—O—C(═O)—.Similarly, the carboxylic anhydride can be converted into the imide,i.e., a ring shown by formula: —C(═O)—N(B¹)—C(═O)— (wherein B¹ has thesame significance as defined above) in a conventional manner of theorganic chemistry.

[0106] n is an integer of not less than 1. When n is 1 and 2, thepolyacene derivative represents a 4-cyclic derivative and a 5-cyclicderivative, namely, a naphthacene derivative and a pentacene derivative,respectively.

[0107] Heretofore, as the number of aromatic rings in condensedpolycyclic aromatic compounds increased, the solubility tended to becomepoor. In the present invention, however, the solubility can bemaintained by introducing a variety of appropriate substituents therein.Thus, n is not limited to 1 and 2 but may be an integer of 3 or more,may be an integer of 4 or more, or may be an integer of 5 or more. Forexample, a 7 benzene ring-condensed polyacene derivative (whichcorresponds to the case wherein n is 4) has been produced.

[0108] n may be 200 or less, 100 or less, 80 or less, 50 or less, 30 orless, 20 or less, 15 or less, or 10 or less, because it is sufficient tosimply repeat this scheme, since the number of n increases two at a timeby applying the process of production later described. And, as describedabove, even though the number of n increases, the solubility can bemaintained by appropriately introducing substituents and thus the numberof n can be increased.

[0109] In the present invention, such compounds that R¹, R², R³, R⁴, R⁵,R⁶, R⁷, R⁸, R⁹, R¹⁰, A¹ and A² are all hydrogen atoms are not intendedas the invention of product, since some of these compounds include thosethat can be isolated from coal or the like and are publicly known.However, the process of producing such compounds falls within thepresent invention.

[0110] In the present invention, when n is 1 in the formula (I) above,the compounds as the invention of product are intended to include thosewherein at least R¹, R², R⁴ and R⁹ are groups other than hydrogen atomor at least R³, R⁵, R⁸ and R¹⁰ are groups other than hydrogen atom, butare not intended to include the cases of (a), (b), (c) and (d) describedbelow.

[0111] (a) when R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, A¹ and A² areall methyl groups;

[0112] (b) when R³, R⁴, R⁹ and R¹⁰ are all aryl groups that mayoptionally be substituted;

[0113] (c) when R¹, R², R⁴ and R⁹ are all alkoxy or aryloxy groups, andR³, R⁵, R⁶, R⁷, R⁸, R¹⁰, A¹ and A² are all hydrogen atoms;

[0114] (d) when R³, R⁵, R⁸ and R¹⁰ are all alkoxy or aryloxy groups, andR¹, R², R⁴, R⁶, R⁷, R⁹, A¹ and A² are all hydrogen atoms.

[0115] Naturally, the process of producing these compounds is within thepresent invention.

[0116] In the present invention, as the invention of product, thecompounds of the formula (I) wherein n is 2 are not intended to includethe cases of (a′), (b′), (c′) and (d′) described below. However, theprocess of producing these compounds is within the present invention.

[0117] (a′) the pentacene derivative represented by formula (Ia) below:

[0118] wherein R¹, R², R³, R⁴, R^(5a), R^(5b), R⁶, R⁷, R^(8a), R^(8b),R⁹, R¹⁰, A¹ and A² are all methyl groups; or R¹, R², R³, R⁴, R^(5a),R^(5b), R^(8a), R^(8b), R⁹, R¹⁰, are all hydrogen atoms and at least oneof R⁶, R⁷, A¹ and A² is an aryl group; or at least one of R¹, R², R³,R⁴, R^(5a), R^(5b), R⁶, R⁷, R^(8a), R^(8b), R⁹, R¹⁰, A¹ and A² is adiarylamine group

[0119] (b′) the pentacene derivative represented by formula (Ib) below:

[0120] wherein R¹, R², R^(5b) and R^(8b) are all alkoxy or aryloxygroups;

[0121] (c′) the pentacene derivative represented by formula (Ic) below:

[0122] wherein at least 2 of R³, R^(5a), R^(8a) and R¹⁰ are aryl orarylalkynyl groups; or at least one of R³, R^(5a), R^(8a) and R¹⁰ is anarylalkenyl group; or R³, R^(5a), R^(8a) and R¹⁰ are all alkoxy oraryloxy groups;

[0123] (d′) the pentacene derivative represented by formula (Id) below:

[0124] wherein R⁴ and R⁹ are hydrogen atom, a hydrocarbon group, analkoxy group, an aryloxy group, a halogen atom or hydroxy group.

[0125] In the polyacene derivatives represented by formula (I),preferably at least 5 of R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, A¹ andA² are groups other than hydrogen atom, more preferably at least 6 ofR¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, A¹ and A² are groups other thanhydrogen atom, much more preferably at least 8 of R¹, R², R³, R⁴, R⁵,R⁶, R⁷, R⁸, R⁹, R¹⁰, A¹ and A² are groups other than hydrogen atom, andmost preferably at least 10 of R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰,A¹ and A² are groups other than hydrogen atom. This is because there isa tendency that as the number of hydrogen atom in R¹, R², R³, R⁴, R⁵,R⁶, R⁷, R⁸, R⁹, R¹⁰, A¹ and A² increases, the yield occasionallydecreases when dehydrogenation is carried out using the combination of alithium dopant and a lithium-removing reagent.

[0126] When the polyacene derivatives represented by formula (I) are thepentacene derivatives shown by formula (Ia) below:

[0127] (wherein R¹, R², R³, R⁴, R^(5a), R^(5b), R⁶, R⁷, R^(8a), R^(8b),R⁹, A¹⁰, A¹ and A² have the same significance as defined above),preferably at least 5 of R¹, R², R³, R⁴, R^(5a), R^(5b), R⁶, R⁷R^(8a),R^(8b), R⁹, R¹⁰, A¹ and A² are groups other than hydrogen atom. Morepreferably, at least 6 of R¹, R², R³, R⁴, R^(5a), R^(5b), R⁶, R⁷,R^(8a), R^(8b), R⁹, R¹⁰, A¹, and A² are groups other than hydrogen atom;further more preferably, at least 7 of R¹, R², R³, R⁴, R^(5a), R^(5b),R⁶, R⁷, R^(8a), R^(8b), R⁹, R¹⁰, A¹ and A² are groups other thanhydrogen atom; much more preferably, at least 8 of R¹, R², R³, R⁴,R^(5a), R^(5b), R⁶, R⁷, R^(8a), R^(8b), R⁹, R¹⁰, A¹ and A² are groupsother than hydrogen atom; further much more preferably, at least 9 ofR¹, R², R³, R⁴, R^(5a), R^(5b), R⁶, R⁷, R^(8a), R^(8b), R⁹, R¹⁰, A¹ andA² are groups other than hydrogen atom; and most preferably, at least 10of R¹, R², R³, R⁴, R^(5a), R^(5b), R⁶, R⁷, R^(8a), R^(8b), R⁹, R¹⁰, A¹and A² are groups other than hydrogen atom.

[0128] In one embodiment of the present invention, any one of thecombinations of R¹ and R², R³ and R¹⁰, R⁴ and R⁵ and R⁶ and R¹, and A¹and A² are preferably the same substituents, and more preferably, R¹ andR² are the same substituents, R³ and R¹⁰ are the same substituents, R⁴and R⁹ are the same substituents, R⁵ and R⁸ are the same substituents,R⁶ and R⁷ are the same substituents, and A¹ and A² are the samesubstituents. This is because it becomes easy to synthesize suchpolyacene derivatives with the improved yield.

[0129] For the same reason, in another aspect of the invention, when thepolyacene derivatives described above are the pentacene derivativesshown by formula (Ia) above, any one of the combinations of R¹ and R²,R³ and R¹⁰, R⁴ and R⁹, R^(5a) and R^(8a), R^(5b) and R^(8b), R⁶ and R⁷,and A¹ and A² are preferably the same substituents, and more preferably,R¹ and R² are the same substituents, R³ and R¹⁰ are the samesubstituents, R⁴ and R⁹ are the same substituents, R^(5a) and R^(8a) arethe same substituents, R^(5b) and R^(8b) are the same substituents, R⁶and R⁷ are the same substituents, and A¹ and A² are the samesubstituents. This is because it becomes easy to synthesize suchpolyacene derivatives with the improved yield.

[0130] Alternatively, from the viewpoints that the synthesis of thepolyacene derivatives becomes easy and the yield is improved, R¹ and R²are preferably the same substituents, R³ and R¹⁰ are preferably the samesubstituents, R⁴ and R⁹ are preferably the same substituents, R⁵ and R⁸(R^(5a) and R^(8a) or R^(5b) and R^(8b) when the polyacene derivativesdescribed above are the pentacene derivatives shown by formula (Ia)above) are preferably the same substituents, R⁶ and R⁷ are preferablythe same substituents, and A¹ and A² are preferably the samesubstituents.

[0131] In one embodiment of the invention, when n is 1, A¹ and A² may bean alkoxycarbonyl group, and R¹, R², R⁴ and R⁹ may be an alkyl or arylgroup. Also, when n is 1, A¹, A², R¹, R², R⁴ and R⁹ may be an alkyl oraryl group. Further when n is 1, A¹ and A² are a halogen atom and R³,R⁵, R⁶, R⁷, R⁸ and R¹⁰ may be an alkyl or aryl group.

[0132] In one embodiment of the present invention, when the polyacenederivatives are the pentacene derivatives represented by the formula(Ia) above, A¹ and A² may be an alkoxycarbonyl group and R¹, R², R⁴,R^(5b), R⁶, R⁷, R^(8b) and R⁹ may be an alkyl or aryl group. Also, whenthe polyacene derivatives are the pentacene derivatives represented bythe formula (Ia) above, A¹, A², R¹, R², R⁴, R^(5b), R⁶, R⁷, R^(8b) andR⁹ may be an alkyl or aryl group. Furthermore, when the polyacenederivatives are the pentacene derivatives represented by the formula(Ia) above, A¹ and A² may be a halogen atom and R³, R^(5a), R^(8a) andR¹⁰ may be an alkyl or aryl group.

[0133] In one aspect of the present invention, there is provided aprocess of producing the polyacene derivatives represented by formula(I) above, which comprises aromatizing the hydrocarbon condensed ringsrepresented by formula (II) below:

[0134] (wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, A¹, R² and nhave the same significance as defined above;

[0135] the bond shown by formula below represents a single bond or adouble bond;

[0136] ), in the presence of a dehydrogenation reagent.

[0137] The hydrocarbon condensed rings shown by formula (II) aboveinclude, e.g., the following hydrocarbon condensed rings represented by(IIa), (IIb) and (IIc), depending upon the kind of bonding:

[0138] (wherein R¹, R², R³, R⁴, R⁵, R^(5a), R^(5b), R⁶, R⁷, R⁸, R^(8a),R^(8b), R⁹, R¹⁰, A¹, A², and n have the same significance as definedabove).

[0139] When n represents an odd number and the hydrocarbon condensedrings shown by formula (II) described above are those shown by formula(IIb) above, k is an integer shown by (n+1)/2, and when n represents aneven number and the hydrocarbon condensed rings shown by formula (II)described above are those shown by formula (IIc) above, m is an integershown by n/2.

[0140] In the hydrocarbon condensed rings shown by formula (IIa), itturns out that one ring is aromatized. On the other hand, in thehydrocarbon condensed rings shown by formula (IIb) and formula (IIc), itturns out that two or more rings are aromatized.

[0141] As a matter of course, the hydrocarbon condensed rings shown byformula (II) also include the cases wherein the rings in a repeatingunit being an aromatic ring and a non-aromatic ring are repeated atrandom.

[0142] In one embodiment of the invention, the dehydrogenation reagentis a combination of a lithium dopant and a lithium-removing reagent. Itis preferred to add the lithium dopant first to the hydrocarboncondensed rings followed by adding the lithium-removing reagent.

[0143] This scheme is illustratively shown with the cases of thehydrocarbon condensed rings shown by formula (IIa), (IIb) and (IIc)below.

[0144] (wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, A¹, A², and nthe same significance as defined above; D¹ represents a nucleophilicgroup such as a C₁-C₆ alkyl group, etc.; D² represents a C₁-C₂₀hydrocarbon group such as a C₁-C₆ alkyl group, etc.; and Z¹ representsan eliminable group such as a halogen atom, etc.).

[0145] In this reaction, R³ and R¹⁰ in formula (IIa) are preferablyhydrogen atoms, in view of easy synthesis of the polyacene derivatives.

[0146] (wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, A¹, A² and khave the same significance as defined above; D¹ represents anucleophilic group such as a C₁-C₆ alkyl group, etc.; D² represents aC₁-C₂₀ hydrocarbon group such as a C₁-C₆ alkyl group, etc.; and Z¹represents an eliminable group such as a halogen atom, etc.).

[0147] In this reaction, R³, R⁵, R⁸ and R¹⁰ in formula (IIb) arepreferably hydrogen atoms, atoms, in view of easy synthesis of thepolyacene derivatives.

[0148] (wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, A¹, A² and mhave the same significance as defined above; D¹ represents anucleophilic group such as a C₁-C₆ alkyl group, etc.; D² represents aC₁-C₂₀ hydrocarbon group such as a C₁-C₆ alkyl group, etc.; and Z¹represents an eliminable group such as a halogen atom, etc.).

[0149] In this reaction, R³, R^(5a), R^(8a) and R¹⁰ in formula (IIc) arepreferably hydrogen atoms, in view of easy synthesis of the polyacenederivatives.

[0150] In the schemes described above, the hydrocarbon condensed ringsrepresented by formula (IIa), (IIb) or (IIc) are employed, for the sakeof explanation to clarify the carbon atoms on which the lithium dopant(IV) shown by Li-D¹ acts. It goes without saying that thedehydrogenation reagent in the combination of the lithium dopant and thelithium-removing reagent is widely applicable to the hydrocarboncondensed rings shown by formula (II) described above.

[0151] The lithium dopant (IV) is reacted with the hydrocarbon condensedrings represented by formulae (IIa), (IIb) and (IIc) to obtain thelithium-provided hydrocarbon condensed rings shown by formula (Va), (Vb)and (Vc), respectively. Preferred lithium dopants include a C₁-C₂₀hydrocarbon lithium such as an alkyl lithium, an aryl lithium, etc. Forexample, a C₁-C₆ alkyl lithium such as butyl lithium, etc., a C₆-C₂₀aryl lithium such as phenyl lithium, etc. are preferably used.

[0152] It is preferred that an activator of the lithium dopant co-existstogether with the lithium dopant (IV). As the activator, tertiary aminesare preferred and, N,N,N′,N′-tetraalkylalkylenediamines such asN,N,N′,N′-tetramethylethylene-diamine (TMEDA), are employed. It islikely that the alkyl lithium would be present in a solution as anoligomer like a tetramer. When a tertiary amine is co-present, it isassumed that the nitrogen atom of the amine would be coordinated on thelithium atom of the alkyl lithium to cleave the oligomer structure,whereby the lithium atom in the alkyl lithium would be exposed to thesolution to improve the reactivity.

[0153] A preferred solvent is an organic solvent. In particular, anon-polar organic solvent is employed. For example, an alkane such ashexane, etc. and an aromatic compound such as benzene, etc. arepreferred.

[0154] A preferred reaction temperature is from 0° C. to 200° C., morepreferably 20° C. to 100° C., and most preferably 30° C. to 80° C.

[0155] When the lithium-removing reagent (VI) is reacted with thehydrocarbon condensed rings shown by formulae (Va), (Vb) and (Vc), it issurmised to form the intermediates shown by formulae (VIIa), (VIIb) and(VIIc), respectively. The intermediates are decomposed to give thepolyacene derivatives shown by formula (I), (Ib) or (Ia).

[0156] As the lithium-removing reagent (VI), for example, alkyl halidesare advantageously used. Preferred examples of alkyl halides are alkylhalides having 6 or less carbon atoms, such as methyl iodide, ethylbromide, etc.

[0157] Where the lithium dopant (IV) and the lithium-removing reagent(VI) having less carbon atoms, such as, butyl lithium and methyl iodideare used as the lithium dopant (IV) and the lithium-removing reagent(VI), respectively, lithium iodide and hexane will be split off. Hexanecan be removed at the same time when the solvent is removed. Lithiumiodide can be removed by washing the resulting reaction mixture withwater. Thus, the combination of the lithium dopant and thelithium-removing reagent renders purification of the reaction mixtureextremely easy and is desirable.

[0158] When a large number of hydrogen atoms are introduced on R¹, R²,R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, A¹ and A², e.g., when at least 8 ofthese groups are hydrogen atoms, the yield of the polyacene derivativeshown by formula (I) based on the hydrocarbon condensed rings of formula(IIa) is approximately 50%. On the other hand, when at least 6,especially 8 or more groups other than hydrogen atom are introduced onR¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R^(10, A) ¹ and A², there is atendency that the yield increases. For example, the yield occasionallyreaches 90% or more, or sometimes becomes 95% or more.

[0159] In another embodiment of the present invention, thedehydrogenation reagent described above is preferably a compound shownby formula (III) below:

[0160] (wherein each of X¹, X², X³ and X⁴, which may be the same ordifferent, independently represents a halogen atom or cyano group).

[0161] The quinones shown by formula (III) above are reacted with thecompounds represented by formula (II) above to become1,4-dihydroxy-cyclohexane derivatives.

[0162] In the quinines shown by formula (III) above, the halogen atom ispreferably chlorine atom, bromine atom or iodine atom, more preferablychlorine atom or bromine atom, and most preferably chlorine atom.

[0163] For example, all of X¹, X², X³ and X⁴ may be chlorine atoms. Thatis, the quinone may be chloranil. Or, X¹ and X² may be cyano group, andX³ and X⁴ may be chlorine atoms. That is, it may be2,3-dichloro-5,6-dicyanoquinone. Or again, X¹, X², X³ and X⁴ may all becyano groups. That is, it may be 2,3,5,6-tetracyanoquinone.

[0164] When the quinones shown by formula (III) above are used, thequinones shown by formula (III) above may occasionally undergoDiels-Alder reaction with the polyacene derivative products to produceby-products. If desired, the by-products are removed by columnchromatography, etc.

[0165] In order to prevent the production of such by-products, thequinones shown by formula (III) above are used preferably in 0.9 to 1.2equivalents, more preferably 0.9 to 1.15 equivalents, and mostpreferably 0.95 to 1.05 equivalents, based on the compounds shown byformula (II) described above.

[0166] As the solvent, an organic solvent is preferred, and an aromaticcompound such as benzene, etc. is particularly preferred.

[0167] The reaction temperature is preferably between −80° C. to 200°C., more preferably 0° C. to 100° C., and most preferably 10° C. to 80°C. If desired, the reaction may be performed under light shielding.

[0168] In other embodiment of the present invention, it is preferredthat the dehydrogenation reagent described above includes palladium. Forexample, palladium carried on carbon such as activated carbon, which iscommercially available as so-called palladium carbon, may preferably beemployed. Pd/C is a catalyst that has been widely used fordehydrogenation, and can be used in the present invention as in aconventional manner. The reaction temperature is, e.g., from 200° C. to500° C. Of course, the reaction temperature may appropriately be setforth, depending upon various conditions such as starting materials,etc.

[0169] The hydrocarbon condensed rings can be obtained, e.g., by thefollowing scheme.

[0170] (wherein R¹, R², R⁴, R⁵, R⁶, R⁷, R⁸, R⁹ and n have the samesignificance as defined above; each of A^(1a) and A^(2a), which may bethe same or different, independently represents a C₆-C₄₀ alkoxycarbonylgroup which may optionally be substituted with a substituent comprisinga halogen atom, or a C₆-C₄₀ aryloxycarbonyl group which may optionallybe substituted a substituent comprising with a halogen atom; and X is aneliminable group such as a halogen atom, etc.;

[0171] the bond shown by formula below represents a single bond or adouble bond;

[0172] M represents a metal belonging to Group III to Group V or alanthanide metal;

[0173] each L¹ and L², which may be the same or different, independentlyrepresents an anionic ligand, provided that L¹ and L² may becross-bridged with each other; and,

[0174] each of Y¹ and Y², which may be the same or different,independently represents an eliminable group).

[0175] (wherein R¹, R², R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, n, A^(1a) and A^(2a)have the same significance as defined above;

[0176] the bond shown by formula below represents a single bond or adouble bond;

[0177] ).

[0178] First, the diester (VIII) is reduced with a reducing agent togive the diol (IX). As the reducing agent, lithium aluminum hydride canbe used. As a solvent, an organic solvent is preferably used, and apolar organic solvent may be used. For example, an ether such as diethylether, THF, etc. may be used.

[0179] The reaction temperature is preferably between −80° C. and 200°C., more preferably between −50° C. and 100° C., and most preferablybetween −20° C. and 80° C. After the reducing agent is added, thereaction may be quenched by adding water, a weak acid, etc.

[0180] If desired, the diester (VIII) may be hydrated under acidic oralkaline conditions to convert into the dicarboxylic acid, thedicarboxylic acid may be reduced to the diketone and then the diketonemay be reduced to the diol.

[0181] Subsequently, the diol (IX) is reacted with a phosphorustrihalide such as phosphorus tribromide, etc., or with SOCl₂, etc. toconvert into the dihalogen (X). It is preferred to use an organicsolvent as the solvent, wherein a polar organic solvent may be used. Forexample, an ether such as THF may be used. The reaction temperature ispreferably between −80° C. and 200° C., more preferably between −50° C.and 100° C., and most preferably between −20° C. and 80° C.

[0182] Next, an alkynyl lithium is reacted with the dihalogen (X) togive the dialkyne (XI). Preferably, the coupling reaction is carried outin the co-presence of a stabilizer such as N,N′-dimethylpropyleneurea,hexamethylphosphamide, etc. As a solvent, it is preferred to use anorganic solvent, in which a polar organic solvent is preferablyemployed. For example, an ether such as THF may be used. The reactiontemperature is preferably between −80° C and 200° C, more preferablybetween −50° C. and 100° C., and most preferably between −20° C. and 80°C.

[0183] The dialkyne (XI) is reacted with an organic metal compound shownby L¹L²MY¹Y² such as a biscyclopentadienylzirconium dialkyl to form themetallacyclopentadiene (XII). The formation of a metallacyclopentadienefrom an organic metal compound shown by L¹L²MY¹Y² is described in, e.g.,T. Takahashi, et al., J. Org. Chem., 1995, 60, 4444, and the reactionproceeds under the same conditions as the literature, or underconditions closely similar to the literature.

[0184] As a solvent, either an aliphatic or aromatic solvent is used,preferably a polar solvent. An ethereal solvent, e.g., tetrahydrofuranor diethyl ether; a halogenated hydrocarbon such as methylene chloride;a halogenated aromatic hydrocarbon such as o-dichiorobenzene; an amidesuch as N,N-dimethylformamide, etc., a sulfoxide such as dimethylsulfoxide, etc., are used. Alternatively, an aromatic hydrocarbon suchas benzene, toluene, xylene, etc. may be used as the aromatic solvent.

[0185] The reaction is preferably carried out at a temperature rangingfrom −80° C. to 300° C., more preferably from 0° C. to 150° C. Thepressure is within 0.1 bar to 2500 bars, preferably within 0.5 bar to 10bars. The reaction may be carried out continuously or batch-wise, in onestep or a multiple step, in a solution or in a suspension, in a gaseousphase or in a supercritical medium.

[0186] M represents a metal belonging to Group III to Group V or alanthanide metal. Preferred examples of M include metals of Group IV orthe lanthanide group in the Periodic Table, more preferably, the metalsof Group IV, namely, titanium, zirconium and hafnium.

[0187] Each L¹ and L², which may be the same or different, independentlyrepresents an anionic ligand.

[0188] The anionic ligand above is preferably a non-localized cyclicη⁵-coordinated ligand, a C₁-C₂₀ alkoxy group, a C₆-C₂₀ aryloxy group ora diakylamide group.

[0189] L¹ and L² is preferably a non-localized cyclic η⁵-coordinatedligand. The non-localized cyclic η⁵-coordinated ligand includesunsubstituted cyclopentadienyl group and a substituted cyclopentadienylgroup. Examples of the substituted cyclopentadienyl group aremethylcyclopentadienyl, ethylcyclopentadienyl,isopropylcyclopentadienyl, n-butylcyclopentadienyl,t-butylcyclopentadienyl, dimethylcyclopentadienyl,diethylcyclopentadienyl, diisopropylcyclopentadienyl,di-t-butylcyclopentadienyl, tetramethylcyclopentadienyl, indenyl,2-methylindenyl, 2-methyl-4-phenylindenyl, tetrahydroindenyl,benzindenyl, fluorenyl, benzofluorenyl, tetrahydrofluorenyl andoctahydrofluorenyl.

[0190] In the non-localized cyclic η⁵-coordinated ligand, one or moreatom(s) in the non-localized cyclic π system may be substituted with ahetero atom(s). In addition to hydrogen, the hetero atoms may includeone or more hetero atoms such as the elements of Group XIV of thePeriodic Table and/or the elements of Groups XV, XVI and XVII of thePeriodic Table.

[0191] The non-localized cyclic η⁵-coordinated ligand, e.g.,cyclopentadienyl group, may form a ring together with the central metal,or may be cross-bridged by one or more cross-bridging ligands. Examplesof the cross-bridging ligands are CH₂, CH₂CH₂, CH(CH₃)CH₂,CH(C₄H₉)C(CH₃)₂, C(CH₃)₂, (CH₃)₂Si, (CH₃)₂Ge, (CH₃)₂Sn, (C₆H₅)₂Si,(C₆H₅)(CH₃)Si, (C₆H₅)₂Ge, (C₆H₅)₂Sn, (CH₂)₄Si, CH₂Si(CH₃)₂, o-C₆H₄ or2,2′-(C₆H₄)₂.

[0192] Two or more non-localized cyclic η⁵-coordinated ligands, e.g.,cyclopentadienyl groups, may be cross-bridged by one or morecross-bridging groups which may contains ring(s). Examples of thecross-bridging groups include CH₂, CH₂CH₂, CH(CH₃)CH₂, CH(C₄H₉)C(CH₃)₂,C(CH₃)₂, (CH₃)₂Si, (CH₃)₂Ge, (CH₃)₂Sn, (C₆H₅)₂Si, (C₆H₅)(CH₃)Si,(C₆H₅)₂Ge, (C₆H₅)₂Sn, (CH₂)₄Si, CH₂Si(CH₃)₂, o-C₆H₄ or 2,2′-(C₆H₄)₂.

[0193] The metallacyclopentadiene further includes compounds containingtwo or more metallacyclopentadiene moieties. Such compounds are known asa polynuclear metallocene. The polynuclear metallocene may take any modeof substitution or any cross-bridged form. In the independentmetallocene moiety of the polynuclear metallocene above, the respectivemoieties may be the same or different. Examples of the polynuclearmetallocene are described in, e.g., EP-A No. 632,063, JPA Nos. H4-80214and H4-85310 and EP-A No. 654,476.

[0194] Each of Y¹ and Y², which may be the same or different,independently represents an eliminable group. Examples of the eliminablegroup include a halogen atom such as F, Cl, Br or I, a C₁-C₂₀ alkylgroup such as n-butyl, etc., a C₆-C₂₀ aryl group such as phenyl, etc.

[0195] The reaction described above is carried out preferably at atemperature ranging from −120° C. to 50° C., more preferably from −120°C. to 0° C.

[0196] Next, in one embodiment of the present invention, themetallacyclopentadiene (XII) is reacted with an alkyne to form a benzenering, whereby the hydrocarbon condensed rings (IId). Typically, analkyne is added to the reaction mixture, without isolating themetallacyclopentadiene (XII).

[0197] A metallacyclopentadiene such as zirconacyclopentadiene isreacted with an alkyne in the presence of CuCl to form a benzene ring,which is described in T. Takahashi, et al., J. Am. Chem. Soc., 1998,120, 1672-1680. The reaction can be proceeded under the same conditionsas the literature, or under conditions closely similar to theliterature.

[0198] Not only CuCl but a metal compound may also be used. Preferably,the metal compound is the metal compound of Groups IV through XV in thePeriodic Table. The metal compound above may be a salt like CuCl or maybe an organic metal complex.

[0199] Examples of the salt include a metal salt such as CuX, NiX₂,PdX₂, ZnX₂, CrX₂, CrX₃, CoX₂ or BiX₃ (wherein X represents a halogenatom such as chlorine atom, bromine atom, etc.).

[0200] As the metal compound, there may be employed an organic metalcomplex, especially a nickel complex. As the organic metal complex,there are employed those wherein ligands such as phosphines; aromaticamines, e.g., pyridine, bipyridine, etc., halogen atoms, or the like arecoordinated to the central metals of Groups III through XI of thePeriodic Table, preferably to the central metals of Groups VI to XI ofthe Periodic Table. The central metals are preferably so-called 4- to6-coordinated, and the metals of Group X in the Periodic Table areparticularly preferred. Phosphines include triphenylphosphine,methyldiphenylphosphine, etc. and are not particularly limited. Examplesof the organic metal complex includebis(triphenylphosphine)dichloronickel, dichloro(2,2′-bipyridyl)nickeland PdCl₂(2,2′-bipyridine). It is described in T. Takahashi, et al., J.Am. Chem. Soc., Vol. 121, No. 48, 1999, 11095 that ametallacyclopentadiene such as zirconacyclopentadiene is reacted with analkyne in the presence of a nickel phosphine complex to form a benzenering.

[0201] The reaction is carried out preferably at a temperature rangingfrom −80° C. to 300° C., more preferably from 0° C. to 150° C. Thepressure is within 0.1 bar to 2500 bars, preferably within 0.5 bar to 10bars. The reaction may be carried out continuously or batch-wise, in onestep or a multiple step, in a solution or in a suspension, in a gaseousphase or in a supercritical medium.

[0202] As a solvent, an aliphatic or aromatic solvent is used,preferably a polar solvent. An ethereal solvent, e.g., tetrahydrofuranor diethyl ether; a halogenated hydrocarbon such as methylene chloride;a halogenated aromatic hydrocarbon such as o-dichlorobenzene; an amidesuch as N,N-dimethylformamide, etc., a sulfoxide such as dimethylsulfoxide, etc., are used.

[0203] The reaction is carried out preferably in the presence of astabilizer, which stabilizes the metal compound in the solvent.Especially when the metal compound is a metal salt and the solvent is anorganic solvent, the stabilizer can stabilize the metal salt in theorganic solvent. Examples of the stabilizer includeN,N′-dimethylpropyleneurea, hexarnethylphosphoamide, tec.

[0204] Then, the hydrocarbon condensed rings (IId) are aromatizedthrough the aromatizing reaction described above to give the polyacenederivative (Ie).

[0205] According to the scheme described above, the polyacene derivative(Ie) wherein R³ and R¹⁰ are hydrogen atoms can be produced. Thepolyacene derivative wherein R³ and R¹⁰ are groups other than hydrogenatom can be produced, e.g., by the following scheme.

[0206] (wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, n, A^(1a) and A^(2a)have the same significance as defined above;

[0207] the bond shown by formula below represents a single bond or adouble bond;

[0208] ).

[0209] The diester (VIIIa) is reduced to the dialdehyde (VIIIb), using areducing agent such as diisobutyl aluminum hydride, etc. Using anorganic solvent, e.g., toluene, etc., the reaction is allowed to proceedat −100° C. to −50° C., preferably at −78° C. It is preferred to useprecisely one equivalent each of the diester and the reducing agent.

[0210] Or, the diester (VIIIa) is hydrolyzed under acidic or basicconditions to form the dicarboxylic acid. The dicarboxylic acid may bereduced to the dialdehyde (VIIIb), using a reducing agent.

[0211] The dialdehyde (VIIIb) is then reacted with Grignard reagent toform the diol (IXa). After that, the diol (IXa) may be reacted asdescribed above.

[0212] Or again, in one embodiment of the present invention, themetallacyclopentadiene (XII) described above may be reacted with anortho-dihalogenoarene such as 1,2-diiodobenzene, or a tetrahalogenoarenesuch as a 1,2,4,5-tetrahalogenobenzene to form the arene ring.

[0213] The coupling reaction is carried out typically in the presence ofa metal compound such as CuCl and a stabilizer. The metal compound ispreferably the metal compound of Groups IV to XV in the Periodic Table.The metal compound described above may be a salt such as CuCl or anorganic metal complex. Examples of the salt include a metal salt such asCuX, NiX₂, PdX₂, ZnX₂, CrX₂, CrX₃, CoX₂ or BiX₃ (wherein X represents ahalogen atom such as chlorine atom, bromine atom, etc.).

[0214] Preferably, a stabilizer such as N,N′-dimethylpropyleneurea,hexamethylphosphoamide, etc. is allowed to be co-present as thestabilizer. As a solvent, it is preferred to use an organic solvent, inwhich a polar organic solvent is preferably employed. For example, anether such as THF may be used. The reaction temperature is preferablybetween −80° C. and 200° C., more preferably between −50° C. and 100°C., and most preferably between −20° C. and 80° C.

[0215] In one embodiment of the present invention, electricallyconductive materials are provided. The form of the conductive materialsis not limited but may be a thin film. The conductive materials maycontain dopants. For example, electron-accepting molecules may beintroduced. In this case, for example, when the thin film is prepared bythe vacuum deposition method, condensed polycyclic aromatic compound aswell as the electron-accepting molecule may be supplied onto a substrateto effect thin film doping. Where the thin film is prepared bysputtering, the sputtering is performed using a binary target of thecondensed polycyclic aromatic compound and the electron-acceptingmolecule to effect the thin film doping. Doping is effected as describedabove. The composition of the conductive material can be varieddepending upon doping conditions. As the dopant, electron-donatingmolecules or electron-accepting molecules, which are used as dopants inconjugated polymers, e.g., polyacetylene, polypyrrole,polyallylenevinylene, polythienylenevinylene, etc. are preferablyemployed.

[0216] When the conductive material is in a thin film, a thickness ofthe film may be prepared in the range of 50 angstrom to the order of amicron, depending upon purpose of using the film. If necessary,protective layers for preventing dopants from spreading/scattering orfor improving mechanical strength or layers of other materials may beprovided on the thin film. Also, a multilayer film consisting of thethin film of the present invention and thin films of other materials maybe used as functional materials by applying thin films thereto.

[0217] The conductivity of the conductive material can be assessed bythe conventional direct current 2-terminal or 4-terminal method. Theconductivity can be varied depending upon the kind or content of dopantsaccording to the purpose of use. The conductivity of the conductivematerial of the present invention is, for example, 10¹⁵ S/cm or more.

[0218] In another aspect of the present invention, there is provided aresin composition, e.g., a blend, comprising the polyacene derivativedescribed above and other synthetic organic polymer. For example, aresin composition comprising 1 wt % to 99 wt % of the polyacenederivative and 99 wt % to 1 wt % of a synthetic organic polymer isprovided. A resin composition comprising 10 wt % to 90 wt % of thepolyacene derivative and 90 wt % to 10 wt % of a synthetic organicpolymer is also provided.

[0219] The synthetic organic polymer includes a thermoplastic polymer, athermosetting polymer, engineering plastics, a conductive polymer, andthe like. The synthetic organic polymer may also be a copolymer.Examples of the thermoplastic polymer include a polyolefin such aspolyethylene, polypropylene, polycycloolefin, ethylene-propylenecopolymer, etc., polyvinyl chloride, polyvinylidene chloride, polyvinylacetate, polyacrylic acid, polymethacrylic acid, polystyrene, polyamide,polyester, polycarbonate, etc. Examples of the thermosetting polymerinclude a phenol resin, a urea resin, a melamine resin, an alkyd resin,an unsaturated polyester resin, an epoxy resin, a silicone resin, apolyurethane resin, etc. Examples of the engineering plastics includepolyimide, polyphenylene oxide, polysulfone, etc. The synthetic organicpolymer may be a synthetic rubber such as styrene-butadiene, etc., or afluoro resin such as polytetrafluoroethylene, etc.

[0220] The conductive polymers include conjugated polymers such aspolyacetylene, polypyrrole, polyallylenevinylene,polythienylenevinylene, etc. and those in which electron-donatingmolecules or electron-accepting molecules are doped. The conductivepolymers further include electron donating molecules such astetrathiafalvalene, bisethylenedithiotetrathiafulvalene, etc., orelectron transfer complexes of such electron-donating molecules incombination with electron accepting molecules such astetracyanoquinodimethane, tetracyanoethylene, etc.

[0221] The resin composition may further contain a variety of additives.Examples of the additives are a plasticizer, an antistatic agent, acolorant, a dopant, etc. Furthermore, the resin composition may alsocontain a reinforcing material such as glass fibers, carbon fibers,aramid fibers, boron fibers, carbon nanotubes, etc.

[0222] The resin composition described above may be prepared into theform of fibers, films or sheets, using methods known to one skilled inthe art. These methods include, but are not limited thereto, meltspinning, spinning from a solution, dry jet wet spinning, extrusion,flow casting and molding techniques. The fibers, films or sheets mayfurther be processed by roll molding, embossing, postforming or othermethods known to one skilled in the art.

[0223] As the organic metal compounds shown by L¹L²MY¹Y², for example,the following compounds may be employed.

[0224] With dihalogeno compounds such asbis(cyclopentadienyl)dichloro-zirconium,bis(methylcyclopentadienyl)dichlorozirconium,bis(butylcyclopentadienyl)dichlorozirconium,bis(indenyl)dichlorozirconium, bis(fluorenyl)dichlorozirconium,(indenyl)(fluorenyl)dichlorozirconium,bis(cyclopentadienyl)dichlorotitanium,(dimethylsilanediyl)bis(indenyl)dichlorozirconium,(dimethylsilanediyl)bis(tetrahydroindenyl)dichlorozirconium,(dimethylsilanediyl)(indenyl)dichlorozirconium,(dimethylsilanediyl)bis(2-methylindenyl)dichlorozirconium,(dimethylsilanediyl)bis(2-ethylindenyl)dichlorozirconium,(dimethylsilanediyl)bis(2-methyl-4,5-benzindenyl)dichlorozirconium,(dimethylsilanediyl)bis(2-ethyl-4,5-benzindenyl)dichlorozirconium,(dimethylsilanediyl)bis(2-methyl-4-phenylindenyl)dichlorozirconium,(dimethylsilanediyl)bis(2-ethyl-4-phenylindenyl)dichlorozirconium,(dimethylsilanediyl)bis(2-methyl-4,6-diisopropylindenyl)dichlorozirconium,it is preferred to form the metallacyclopentadienes either afterreducing the dihalogeno compounds with a strong base such as an alkalimetal, e.g., sodium, etc., an alkaline earth metal such as magnesium,etc. or after converting the dihalogeno compounds into the dialkylcompounds.

[0225] bis(cyclopentadienyl)dibutylzirconium;

[0226] bis(butylcyclopentadienyl)dibutylzirconium;

[0227] bis(methylcyclopentadienyl)dibutylzirconium;

[0228] bis(indenyl)dibutylzirconium;

[0229] bis(fluorenyl)dibutylzirconium;

[0230] (indenyl)(fluorenyl)dibutylzirconium;

[0231](3-methyl-5-naphthylindenyl)(2,7-di-tert-butylfluorenyl)dibutylzirconium;

[0232](3-methyl-5-naphthylindenyl)(3,4,7-trimethoxyfluorenyl)dibutylzirconium;

[0233] (pentamethylcyclopentadienyl)(tetrahydroindenyl)dibutylzirconium;

[0234] (cyclopentadienyl)(1-octene-8-ylcyclopentadienyl)dibutylzirconium;

[0235] (indenyl)( 1-butene-4-ylcyclopentadienyl)dibutylzirconium;

[0236][1,3-bis(trimethylsilyl)cyclopentadienyl](3,4-benzofluorenyl)dibutylzirconium;

[0237] bis(cyclopentadienyl)dibutyltitanium;

[0238] dimethylsilanediylbis(indenyl)dibutylzirconium;

[0239] dimethylsilanediylbis(tetrahydroindenyl)dibutylzirconium;

[0240] dimethylsilanediyl(cyclopentadienyl)(indenyl)dibutylzirconium;

[0241] dimethylsilanediylbis(2-methylindenyl)dibutylzirconium;

[0242] dimethylsilanediylbis(2-ethylindenyl)dibutylzirconium;

[0243] dimethylsilanediylbis(2-methyl-4,5-benzindenyl)dibutylzirconium;

[0244] dimethylsilanediylbis(2-ethyl-4,5-benzindenyl)dibutylzirconium;

[0245]dimethylsilanediylbis(4,5-dihydro-8-methyl-7H-cyclopent[e]acenaphthylene-7-ylidene)dibutylzirconium;

[0246]dimethylsilanediyl(2-methyl-4,5-benzindenyl)(2-methyl-4-phenylindenyl)dibutylzirconium;

[0247]dimethylsilanediyl(2-ethyl-4,5-benzindenyl)(2-methyl-4-phenylindenyl)dibutylzirconium;

[0248]dimethylsilanediyl(2-methyl-4,5-benzindenyl)(2-ethyl-4-phenylindenyl)dibutylzirconium;

[0249]dimethylsilanediyl(2-ethylindenyl)(2-ethyl-4-phenylnaphthyl)dibutylzirconium;

[0250]dimethylsilanediyl(2-methylindenyl)(4-phenylindenyl)dibutylzirconium;

[0251] dimethylsilanediylbis(2-methyl-4-phenylindenyl)dibutylzirconium;

[0252] dimethylsilanediylbis(2-ethyl-4-phenylindenyl)dibutylzirconium;

[0253]dimethylsilanediylbis(2-methyl-4,6-diisopropylindenyl)dibutylzirconium;

[0254]dimethylsilanediylbis(2-ethyl-4,6-diisopropylindenyl)dibutylzircomium;

[0255]dimethylsilanediylbis(2-methyl-4-naphthylindenyl)dibutylzirconium;

[0256] dimethylsilanediylbis(2-ethyl-4-naphthylindenyl)dibutylzirconium;

[0257] methylphenylsilanediylbis(indenyl)dibutylzirconium;

[0258]methylphenylsilanediyl(cyclopentadienyl)(indenyl)dibutylzirconium;

[0259] methylphenylsilanediylbis(tetrahydroindenyl)dibutylzirconium;

[0260] methylphenylsilanediylbis(2-methylindenyl)dibutylzirconium;

[0261] methylphenylsilanediylbis(2-ethylindenyl)dibutylzirconium;

[0262]methylphenylsilanediylbis(2-methyl-4,5-benzindenyl)dibutylzirconium;

[0263]methylphenylsilanediylbis(2-ethyl-4,5-benzindenyl)dibutylzirconium;

[0264]methylphenylsilanediylbis(4,5-dihydro-8-methyl-7H-cyclopent[e]acenaphthylene-7-ylidene)dibutylzirconium;

[0265]methylphenylsilanediyl(2-methyl-4,5-benzindenyl)(2-methyl-4-phenylindenyl)dibutylzirconium;

[0266]methylphenylsilanediyl(2-ethylindenyl)(2-methyl-4-phenylindenyl)dibutylzirconium;

[0267]methylphenylsilanediyl(2-methyl-4,5-benzindenyl)(2-ethyl-4-phenylindenyl)dibutylzirconium;

[0268]methylphenylsilanediyl(2-ethyl-4,5-benzindenyl)(2-ethyl-indenyl)dibutylzirconium;

[0269]methylphenylsilanediyl(2-methylindenyl)(4-phenylindenyl)dibutylzirconium;

[0270]methylphenylsilanediylbis(2-methyl-4-phenylindenyl)dibutylzirconium;

[0271] methylphenylsilanediylbisdibutylzirconium;

[0272]methylphenylsilanediylbis(2-methyl-4,6-diisopropylindenyl)dibutylzirconium;

[0273]methylphenylsilanediylbis(2-ethyl-4,6-diisopropylindenyl)dibutylzirconium;

[0274] methylphenylsilanediylbis(4-naphthylindenyl)dibutylzirconium;

[0275]methylphenylsilanediylbis(2-ethyl-4-naphthylindenyl)dibutylzirconium;

[0276] diphenylsilanediylbis(indenyl)dibutylzirconium;

[0277] diphenylsilanediylbis(2-methylindenyl)dibutylzirconium;

[0278] diphenylsilanediylbis(2-ethylindenyl)dibutylzirconium;

[0279] diphenylsilanediyl(cyclopentadienyl)(indenyl)dibutylzirconium;

[0280] diphenylsilanediylbis(2-methyl-4,5-benzindenyl)dibutylzirconium;

[0281] diphenylsilanediylbis(2-ethyl-4,5-benzindenyl)dibutylzirconium;

[0282]diphenylsilanediyl(2-methyl-4,5-benzindenyl)(2-methyl-4-phenylindenyl)dibutylzirconium;

[0283]diphenylsilanediyl(2-ethyl-4,5-benzindenyl)(2-methyl-4-phenylindenyl)dibutylzirconium;

[0284]dihenylsilanediyl(2-methyl-4,5-benzindenyl)(2-ethyl-4-phenylindenyl)dibutylzirconium;

[0285]diphenylsilanediyl(2-ethyl-4,5-benzindenyl)(2-ethyl-4-naphthylindenyl)dibutylzirconium;

[0286]diphenylsilanediyl(2-methylindenyl)(4-phenylindenyl)dibutylzircorium;

[0287] diphenylsilanediylbis(2-methyl-4-phenylindenyl)dibutylzirconium;

[0288] diphenylsilanediylbis(2-ethyl-4-phenylindenyl)dibutylzirconium;

[0289]diphenylsilanediylbis(2-methyl-4,6-diisopropylindenyl)dibutylzirconium;

[0290]diphenylsilanediylbis(2-ethyl-4,6-diisopropylindenyl)dibutylzirconium;

[0291]diphenylsilanediylbis(2-methyl-4-naphthylindenyl)dibutylzirconium;

[0292] diphenylsilanediylbis(2-ethyl-4-naphthylindenyl)dibutylzirconium;

[0293] 1-silacyclopentane-1,1-bis(indenyl)dibutylzirconium;

[0294] 1-silacyclopentane-1,1-bis(2-methylindenyl)dibutylzirconium;

[0295] 1-silacyclopentane-1,1-bis(2-ethylindenyl)dibutylzirconium;

[0296]1-silacyclopentane-1,1-bis(2-methyl-4,5-benzindenyl)dibutylzirconium;

[0297]1-silacyclopentane-1,1-bis(2-ethyl-4,5-benzindenyl)dibutylzirconium;

[0298]1-silacyclopentane-1-(2-methyl-4,5-benzindenyl)-1-(2-methyl-4-phenylindenyl)dibutylzirconium;

[0299]1-silacyclopentane-1-(2-ethyl-4,5-benzindenyl)-1-(2-methyl-4-phenylindenyl)dibutylzirconium;

[0300]1-silacyclopentane-1-(2-methyl-4,5-benzindenyl)-1-(2-ethyl-4-phenylindenyl)dibutylzirconium;

[0301]1-silacyclopentane-1-(2-ethyl-4,5-benzindenyl)-1-(2-ethyl-4-naphthylindenyl)dibutylzirconium;

[0302]1-silacyclopentane-1-(2-methylindenyl)-1-(4-phenylindenyl)dibutylzirconium;

[0303]1-silacyclopentane-1,1-bis(2-methyl-4-phenylindenyl)dibutylzirconium;

[0304]1-silacyclopentane-1,1-bis(2-ethyl-4-phenylindenyl)dibutylzirconium;

[0305]1-silacyclopentane-1,1-bis(2-methyl-4,6-diisopropylindenyl)dibutylzirconium;

[0306]1-silacyclopentane-1,1-bis(2-ethyl-4,6-diisopropylindenyl)dibutylzirconium;

[0307]1-silacyclopentane-1,1-bis(2-methyl-4-naphthylindenyl)dibutylzirconium;

[0308]1-silacyclopentane-1,1-bis(2-ethyl-4-naphthylindenyl)dibutylzirconium;

[0309] ethylene-1,2-bis(indenyl)dibutylzirconium;

[0310] ethylene-1,2-bis(tetrahydroindenyl)dibutylzirconium;

[0311] ethylene-1-(cyclopentadienyl)-2-(1-indenyl)dibutylzirconium;

[0312] ethylene-1-(cyclopentadienyl)-2-(2-indenyl)dibutylzirconium;

[0313]ethylene-1-(cyclopentadienyl)-2-(2-methyl-1-indenyl)dibutylzirconium;

[0314] ethylene-1,2-bis(2-methylindenyl)dibutylzirconium;

[0315] ethylene-1,2-bis(2-ethylindenyl)dibutylzirconium;

[0316] ethylene-1,2-bis(2-methyl-4,5-benzindenyl)dibutylzirconium;

[0317] ethylene-1,2-bis(2-ethyl-4,5-benzindenyl)dibutylzirconium;

[0318]ethylene-1,2-bis(4,5-dihydro-8-methyl-7H-cyclopent[e]acenaphthylene-7-ylidene)dibutylzirconium;

[0319]ethylene-1-(2-methyl-4,5-benzindenyl)-2-(2-methyl-4-phenylindenyl)dibutylzirconium;

[0320]ethylene-1-(2-ethyl-4,5-benzindenyl)-2-(2-methyl-4-phenylindenyl)dibutylzirconium;

[0321]ethylene-1-(2-methyl-4,5-benzindenyl)-2-(2-ethyl-4-phenylindenyl)dibutylzirconium;

[0322]ethylene-1-(2-ethyl-4,5-benzindenyl)-2-(2-ethyl-4-naphthylindenyl)dibutylzirconium;

[0323] ethylene-1-(2-methylindenyl)-2-(4-phenylindenyl)dibutylzirconium;

[0324] ethylene-1,2-bis(2-methyl-4-phenylindenyl)dibutylzirconium;

[0325] ethylene-1,2-bis(2-ethyl-4-phenylindenyl)dibutylzirconium;

[0326]ethylene-1,2-bis(2-methyl-4,6-diisopropylindenyl)dibutylzirconium;

[0327] ethylene-1,2-bis(2-ethyl-4,6-diisopropylindenyl)dibutylzirconium;

[0328] ethylene-1,2-bis(2-methyl-4-naphthylindenyl)dibutylzirconium;

[0329] ethylene-1,2-bis(2-ethyl-4-naphthylindenyl)dibutylzirconium;

[0330] propylene-2,2-bis(indenyl)dibutylzirconium;

[0331] propylene-2-cyclopentadienyl-2-(1-indenyl)dibutylzirconium;

[0332]propylene-2-cyclopentadienyl-2-(4-phenyl-1-indenyl)dibutylzirconium;

[0333] propylene-2-cyclopentadienyl-2-(9-fluorenyl)dibutylzirconium;

[0334]propylene-2-cyclopentadienyl-2-(2,7-dimethoxy-9-fluorenyl)dibutylzirconium;

[0335]propylene-2-cyclopentadienyl-2-(2,7-di-tert-butyl-9-fluorenyl)dibutylzirconium;

[0336]propylene-2-cyclopentadienyl-2-(2,7-dibromo-9-fluorenyl)dibutylzirconium;

[0337]propylene-2-cyclopentadienyl-2-(2,7-diphenyl-9-fluorenyl)dibutylzirconium;

[0338]propylene-2-cyclopentadienyl-2-(2,7-dimethyl-9-fluorenyl)dibutylzirconium;

[0339]propylene-2-(3-methylcyclopentadienyl)-2-(2,7-dibutyl-9-fluorenyl)dibutylzirconium;

[0340]propylene-2-(3-tert-butylcyclopentadienyl)-2-(2,7-dibutyl-9-fluorenyl)dibutylzirconium;

[0341] propylene-2-(3-trimethylsilylcyclopentadienyl)-2-(3,6-di-tert-butyl-9-fluorenyl)dibutylzirconium;

[0342]propylene-2-cyclopentadienyl-2-[2,7-bis(3-butene-1-yl)-9-fluorenyl]dibutylzirconium;

[0343]propylene-2-cyclopentadienyl-2-(3-tert-butyl-9-fluorenyl)dibutylzirconium;

[0344] propylene-2,2-bis(tetrahydroindenyl)dibutylzirconium;

[0345] propylene-2,2-bis(2-methylindenyl)dibutylzirconium;

[0346] propylene-2,2-bis(2-ethylindenyl)dibutylzirconium;

[0347] propylene-2,2-bis(2-methyl-4,5-benzindenyl)dibutylzirconium;

[0348] propylene-2,2-bis(2-ethyl-4,5-benzindenyl)dibutylzirconium;

[0349]propylene-2,2-bis(4,5-dihydro-8-methyl-7H-cyclopent[e]acenaphthylene-7-ylidene)dibutylzirconium;

[0350]propylene-2-(2-methyl-4,5-benzindenyl)-2-(2-methyl-4-phenylindenyl)dibutylzirconium;

[0351]propylene-2-(2-ethyl-4,5-benzindenyl)-2-(2-methyl-4-phenylindenyl)dibutylzirconium;

[0352]propylene-2-(2-methyl-4,5-benzindenyl)-2-(2-ethyl-4-phenylindenyl)dibutylzirconium;

[0353]propylene-2-(2-ethyl-4,5-benzindenyl)-2-(2-ethyl-4-naphthylindenyl)dibutylzirconium;

[0354]propylene-2-(2-methylindenyl)-2-(4-phenylindenyl)dibutylzirconium;

[0355] propylene-2,2-bis(2-methyl-4-phenylindenyl)dibutylzirconium;

[0356] propylene-2,2-bis(2-ethyl-4-phenylindenyl)dibutylzirconium;

[0357]propylene-2,2-bis(2-methyl-4,6-diisopropylindenyl)dibutylzirconium;

[0358]propylene-2,2-bis(2-ethyl-4,6-diisopropylindenyl)dibutylzirconium;

[0359] propylene-2,2-bis(2-methyl-4-naphthylindenyl)dibutylzirconium;

[0360] propylene-2,2-bis(2-ethyl-4-naphthylindenyl)dibutylzirconium;

[0361]1,6-bis[methylsilylbis(2-methyl-4-phenylindenyl)dibutylzirconium]hexane;

[0362]1,6-bis[methylsilylbis(2-methyl-4,5-benzindenyl)dibutylzirconium]hexane;

[0363]1,6-bis[methylsilylbis(2-ethyl-4-phenylindenyl)dibutylzirconium]hexane;

[0364]1,6-bis[methylsilylbis(2-methyl-4-naphthylindenyl)dibutylzirconium]hexane;

[0365]1,6-bis[methylsilylbis(2-methyl-4,6-diisopropylindenyl)dibutylzirconium]hexane;

[0366]1,6-bis[methylsilyl(2-methyl-4-phenylindenyl)(4,5-benzindenyl)dibutylzirconium]hexane;

[0367]1-[methylsilylbis(tetrahydroindenyl)dibutylzirconium]-6-[ethylstannyl(cyclopentadienyl)(fluorenyl)dibutylzirconium]hexane;

[0368]1,6-disila-1,1,6,6-tetramethyl-1,6-bis[methylsilylbis(2-methyl-4-phenylindenyl)dibutylzirconium]hexane;

[0369]1,4-disila-1,4-bis[methylsilylbis(2-methyl-4-phenylindenyl)dibutylzirconium]cyclohexane;

[0370][1,4-bis(1-indenyl)-1,1,4,4-tetramethyl-1,4-disilabutane]bis(pentamethylcyclopentadienyldibutylzirconium);

[0371][1,4-bis(9-fluorenyl)-1,1,4,4-tetramethyl-1,4-disilabutane]bis(cyclopentadienyldibutylzirconium);

[0372][1,4-bis(1-indenyl)-1,1,4,4-tetramethyl-1,4-disilabutane]bis(cyclopentadienyldibutylzirconium);

[0373][1-(1-indenyl)-6-(2-phenyl-1-indenyl)-1,1,6,6-tetraethyl-1,6-disila-4-oxahexane]bis(tert-butylcyclopentadienyldibutylzirconium);

[0374][1,10-bis(2,3-dimethyl-1-indenyl)-1,1,10,10-tetramethyl-1,10-digermadecane]bis(2-methyl-4-phenylindenyldibutylzirconium);

[0375](1-methyl-3-tert-butylcyclopentadienyl)(1-phenyl-4-methoxy-7-chlorofluorenyl)dibutylzirconium;

[0376] (4,7-dichloroindenyl)(3,6-dimesitylfluorenyl)dibutylzirconium;

[0377] bis(2,7-di-tert-butyl-9-cyclohexylfluorenyl)dibutylzirconium;

[0378](2,7-dimesitylfluorenyl)[2,7-bis(1-naphthyl)fluorenyl]dibutylzirconium;

[0379] dimethylsilylbis(fluorenyl)dibutylzirconium;

[0380] dibutylstannylbis(2-methylfluorenyl)dibutylzirconium;1,1,2,2-tetraethyldisilanediyl(2-methylindenyl)(4-phenylfluorenyl)dibutylzirconium;

[0381] propylene-1-(2-indenyl)-2-(9-fluorenyl)dibutylzirconium;

[0382] 1,1-dimethyl-1-silaethylenebis(fluorenyl)dibutylzirconium;

[0383][4-(cyclopentadienyl)-4,7,7-trimethyl(tetrahydroindenyl)dibutylzirconium;

[0384][4-(cyclopentadienyl)-4,7-dimethyl-7-phenyl(5,6-dimethyltetrahydroindenyl)dibutylzirconium;

[0385][4-(cyclopentadienyl)-4,7-dimethyl-7-(1-naphthyl)(7-phenyltetrahydroindenyl)]dibutylzirconium;

[0386][4-(cyclopentadienyl)-4,7-dimethyl-7-butyl(6,6-diethyltetrahydroindenyl)]dibutylzirconium;

[0387][4-(3-tert-butylcyclopentadienyl)-4,7,7-trimethyl(tetrahydroindenyl)dibutylzirconium;

[0388][4-(1-indenyl)-4,7,7-trimethyl(tetrahydroindenyl)]dibutylzirconium;

[0389] bis(cyclopentadienyl)dibutylhafnium;

[0390] bis(indenyl)dibutylvanadium;

[0391] bis(fluorenyl)dibutylscandium;

[0392] (indenyl)(fluorenyl)dibutylniobium;

[0393](2-methyl-7-naphthylindenyl)(2,6-di-tert-butylfluorenyl)dibutyltitanium;

[0394] (pentamethylcyclopentadienyl)(tetrahydroindenyl)butylhaffniumbromide;

[0395] (cyclopentadienyl)(1-octene-8-ylcyclopentadienyl)dibutylhafnium;

[0396] (indenyl)(2-butene-4-ylcyclopentadienyl)dibutyltitanium;

[0397][1,3-bis(trimethylsilyl)cyclopentadienyl](3,4-benzofluorenyl)dibutylniobium;

[0398] dimethylsilanediylbis(indenyl)dibutyltitanium;

[0399] dimethylsilanediylbis(tetrahydroindenyl)dibutylhafnium;

[0400] dimethylsilanediyl(cyclopentadienyl)(indenyl)dibutyltitanium;

[0401] dimethylsilanediylbis(2-m ethylindenyl)dibutylhafnium;

[0402] dimethylsilanediylbis(2-ethylindenyl)methylscandium;

[0403] dimethylsilanediylbis(2-butyl-4,5-benzindenyl)dibutylniobium;

[0404] dimethylsilanediylbis(2-ethyl-4,5-benzindenyl)dibutyltitanium;

[0405]dimethylsilanediylbis(4,5-dihydro-8-methyl-7H-cyclopent[e]acenaphthylene-7-ylidene)dibutyltianium;

[0406]dimethylsilanediyl(2-methyl-4,5-benzindenyl)(2-methyl-4-phenylindenyl)dibutyltitanium;

[0407]dimethylsilanediyl(2-ethyl-4,5-benzindenyl)(2-methyl-4-phenylindenyl)dibutylhafnium;

[0408]dimethylsilanediyl(2-ethyl-4,5-benzindenyl)(2-ethyl-4-phenylindenyl)methylscandium;

[0409]dimethylsilanediyl(2-ethyl-4,5-benzindenyl)(2-ethyl-4-naphthylindenyl)dibutyltitanium;

[0410]dimethylsilanediyl(2-methylindenyl)(4-phenylindenyl)dibutylhafnium;

[0411] dimethylsilanediylbis(2-methyl-4-phenylindenyl)dibutylniobium;

[0412] dimethylsilanediylbis(2-ethyl-4-phenylindenyl)dibutylvanadium;

[0413]dimethylsilanediylbis(2-methyl-4,6-diisopropylindenyl)dibutylhafnium;

[0414]dimethylsilanediylbis(2-ethyl-4,6-diisopropylindenyl)dibutylvanadium;

[0415] dimethylsilanediylbis(2-methyl-4-naphthylindenyl)butylhaffniumbromide;

[0416] dimethylsilanediylbis(2-ethyl-4-naphthylindenyl)dibutyltitanium;

[0417] methylphenylsilanediylbis(indenyl)dibutyltitanium;

[0418] methylphenylsilanediyl(cyclopentadienyl)(indenyl)hafnium;

[0419] methylphenylsilanediylbis(tetrahydroindenyl)dibutylhafnium;

[0420] methylphenylsilanediylbis(2-methylindenyl)dibutyltitanium;

[0421] methylphenylsilanediylbis(2-ethylindenyl)dibutylhafnium;

[0422]methylphenylsilanediylbis(2-methyl-4,5-benzindenyl)dibutylhafnium;

[0423]methylphenylsilanediylbis(2-ethyl-4,5-benzindenyl)dibutylvanadium;

[0424]methylphenylsilanediylbis(4,5-dihydro-8-methyl-7H-cyclopent[e]acenaphthylene-7-ylidene)dibutyltitanium;

[0425]methylphenylsilanediylbis(2-methyl-4,5-benzindenyl)(2-methyl-4-phenylindenyl)butyltitaniumbromide;

[0426]methylphenylsilanediylbis(2-ethyl-4,5-benzindenyl)(2-methyl-4-phenylindenyl)dibutyltitanium;

[0427]methylphenylsilanediylbis(2-methyl-4,5-benzindenyl)(2-ethyl-4-phenylindenyl)dibutylhafnium;

[0428]methylphenylsilanediylbis(2-ethyl-4,5-benzindenyl)(2-ethyl-4-phenylindenyl)dibutylhafnium;

[0429]methylphenylsilanediyl(2-methylindenyl)(4-phenylindenyl)dibutyltitanium;

[0430]methylphenylsilanediylbis(2-methyl-4-phenylindenyl)dibutylhafnium;

[0431]methylphenylsilanediylbis(2-ethyl-4-phenylindenyl)dibutylvanadium;

[0432]methylphenylsilanediylbis(2-methyl-4,6-diisopropylindenyl)dibutyltitanium;

[0433]methylphenylsilanediylbis(2-ethyl-4,6-diisopropylindenyl)dibutylhafnium;

[0434]methylphenylsilanediylbis(2-methyl-4-naphthylindenyl)dibutylhafnium;

[0435]methylphenylsilanediylbis(2-ethyl-4-naphthylindenyl)dibutyltitanium;

[0436] diphenylsilanediylbis(indenyl)dibutyltitanium;

[0437] diphenylsilanediylbis(2-methylindenyl)dibutylhafnium;

[0438] diphenylsilanediylbis(2-ethylindenyl)dibutyltitanium;

[0439] diphenylsilanediylbis(cyclopentadienyl)(indenyl)dibutylhafnium;

[0440] diphenylsilanediylbis(2-methyl-4,5-benzindenyl)dibutyltitanium;

[0441] diphenylsilanediylbis(2-ethyl-4,5-benzindenyl)dibutylhafnium;

[0442]diphenylsilanediyl(2-methyl-4,5-benzindenyl)(2-methyl-4,5-phenylindenyl)dibutylhafnium;

[0443]diphenylsilanediyl(2-ethyl-4,5-benzindenyl)(2-methyl-4,5-phenylindenyl)dibutyltitanium;

[0444]diphenylsilanediyl(2-methyl-4,5-benzindenyl)(2-ethyl-4,5-phenylindenyl)dibutylhafnium;

[0445]diphenylsilanediyl(2-ethyl-4,5-benzindenyl)(2-ethyl-4,5-phenylindenyl)dibutyltitanium;

[0446]diphenylsilanediyl(2-methylindenyl)(4-phenylindenyl)dibutyltitanium;

[0447] diphenylsilanediylbis(2-methyl-4-phenylindenyl)dibutyltitanium;

[0448] diphenylsilanediylbis(2-ethyl-4-phenylindenyl)dibutylhafnium;

[0449]diphenylsilanediylbis(2-methyl-4,6-diisopropylindenyl)dibutylhafnium;

[0450]diphenylsilanediylbis(2-ethyl-4,6-diisopropylindenyl)dibutylhafnium;

[0451] diphenylsilanediylbis(2-methyl-4-naphthylindenyl)dibutylhafnium;

[0452] diphenylsilanediylbis(2-ethyl-4-naphthylindenyl)dibutyltitanium;

[0453] 1-silacyclopentane-1,1-bis(indenyl)dibutylhafnium;

[0454] 1-silacyclopentane-1,1-bis(2-methylindenyl)dibutylhafnium;

[0455] 1-silacyclopentane-1,1-bis(2-ethylindenyl)dibutylhafnium;

[0456]1-silacyclopentane-1,1-bis(2-methyl-4,5-benzindenyl)dibutyltitanium;

[0457]1-silacyclopentane-1,1-bis(2-ethyl-4,5-benzindenyl)dibutylhafnium;

[0458]1-silacyclopentane-1-(2-methyl-4,5-benzindenyl)-1-(2-methyl-4-phenylindenyl)methylscandium;

[0459]1-silacyclopentane-1-(2-ethyl-4,5-benzindenyl)-1-(2-methyl-4-phenylindenyl)dibutylhafnium;

[0460]1-silacyclopentane-1-(2-methyl-4,5-benzindenyl)-1-(2-ethyl-4-phenylindenyl)dibutyltitanium;

[0461]1-silacyclopentane-1-(2-ethyl-4,5-benzindenyl)-1-(2-ethyl-4-phenylindenyl)dibutylhafnium;

[0462]1-silacyclopentane-1-(2-methylindenyl)-1-(4-phenylindenyl)dibutylhafnium;

[0463]1-silacyclopentane-1,1-bis(2-methyl-4-phenylindenyl)dibutylhafnium;

[0464]1-silacyclopentane-1,1-bis(2-ethyl-4-phenylindenyl)dibutyltitaniumbromide;

[0465]1-silacyclopentane-1,1-bis(2-methyl-4,6-diisopropylindenyl)dibutyltitanium;

[0466]1-silacyclopentane-1,1-bis(2-ethyl-4,6-diisopropylindenyl)dibutyltitanium;

[0467]1-silacyclopentane-1,1-bis(2-methyl-4-naphthylindenyl)methylscandium;

[0468]1-silacyclopentane-1,1-bis(2-ethyl-4-naphthylindenyl)dibutylhafnium;

[0469] ethylene-1,2-bis(indenyl)methylscandium;

[0470] ethylene-1,2-bis(tetrahydroindenyl)dibutyltitanium;

[0471] ethylene-1-(cyclopentadienyl)-2-(1-indenyl)dibutylhafnium;

[0472] ethylene-1-(cyclopentadienyl)-2-(2-indenyl)butyltitanium bromide;

[0473]ethylene-1-(cyclopentadienyl)-2-(2-methyl-1—indenyl)dibutylhafnium;

[0474] ethylene-1,2-bis(2-methylindenyl)dibutylhafnium;

[0475] ethylene-1,2-bis(2-ethylindenyl)dibutylhafnium;

[0476] ethylene-1,2-bis(2-methyl-4,5-benzindenyl)dibutylhafnium;

[0477] ethylene-1,2-bis(2-ethyl-4,5-benzindenyl)dibutyltitanium;

[0478]ethylene-1,2-bis(4,5-dihydro-8-methyl-7H-cyclopent[e]acenaphthylene-7-ylidene)dibutyltitanium;

[0479]ethylene-1-(2-methyl-4,5-benzindenyl)-2-(2-methyl-4-phenylindenyl)dibutyltitanium;

[0480]ethylene-1-(2-ethyl-4,5-benzindenyl)-2-(2-methyl-4-phenylindenyl)dibutyltitanium;

[0481]ethylene-1-(2-methyl-4,5-benzindenyl)-2-(2-ethyl-4-phenylindenyl)methylscandium;

[0482]ethylene-1-(2-ethyl-4,5-benzindenyl)-2-(2-ethyl-4-naphthylindenyl)dibutylhafnium;

[0483] ethylene-1-(2-methylindenyl)-2-(4-phenylindenyl)dibutyltitanium;

[0484] ethylene-1,2-bis(2-methyl-4-phenylindenyl)dibutylhafnium;

[0485] ethylene-1,2-bis(2-ethyl-4-phenylindenyl)dibutylhafnium;

[0486] ethylene-1,2-bis(2-methyl-4,6-diisopropylindenyl)dibutylhafnium;

[0487] ethylene-1,2-bis(2-ethyl-4,6-diisopropylindenyl)dibutyltitanium;

[0488] ethylene-1,2-bis(2-methyl-4-naphthylindenyl)dibutyltitanium;

[0489] ethylene-1,2-bis(2-ethyl-4-naphthylindenyl)dibutylhafnium;

[0490] propylene-2,2-bis(indenyl)dibutylhafnium;

[0491] propylene-2-cyclopentadienyl-2-( 1-indenyl)dibutyltitanium;

[0492]propylene-2-cyclopentadienyl-2-(4-phenyl-1-indenyl)dibutyltitanium;

[0493] propylene-2-cyclopentadienyl-2-(9-fluorenyl)dibutylhafnium;

[0494]propylene-2-cyclopentadienyl-2-(2,7-dimethoxy-9-fluorenyl)dibutylhafnium;

[0495]propylene-2-cyclopentadienyl-2-(2,7-di-tert-butyl-9-fluorenyl)dibutylhafnium;

[0496]propylene-2-cyclopentadienyl-2-(2,7-dibromo-9-fluorenyl)dibutyltitanium;

[0497]propylene-2-cyclopentadienyl-2-(2,7-diphenyl-9-fluorenyl)dibutylhafnium;

[0498]propylene-2-cyclopentadienyl-2-(2,7-dimethyl-9-fluorenyl)dibutyltitanium;

[0499]propylene-2-(3-methylcyclopentadienyl)-2-(2,7-dibutyl-9-fluorenyl)dibutylhafnium;

[0500]propylene-2-(3-tert-butylcyclopentadienyl)-2-(2,7-dibutyl-9-fluorenyl)dibutyltitanium;

[0501]propylene-2-(3-trimethylsilylcyclopentadienyl)-2-(3,6-di-tert-butyl-9-fluorenyl)dibutyltitanium;

[0502]propylene-2-cyclopentadienyl-2-[2,7-bis(3-butene-1-yl)-9-fluorenyl]dibutylhafnium;

[0503]propylene-2-cyclopentadienyl-2-(3-tert-butyl-9-fluorenyl)dibutyltitanium;

[0504] propylene-2,2-bis(tetrahydroindenyl)dibutylhafnium;

[0505] propylene-2,2-bis(2-methylindenyl)dibutylhafnium;

[0506] propylene-2,2-bis(2-ethylindenyl)dibutyltitanium;

[0507] propylene-2,2-bis(2-methyl-4,5-benzindenyl)dibutyltitanium;

[0508] propylene-2,2-bis(2-ethyl-4,5-benzindenyl)dibutylhafnium;

[0509]propylene-2,2-bis(4,5-dihydro-8-methyl-7H-cyclopent[e]acenaphthylene-7-ylidene)dibutylhafnium;

[0510]propylene-2-(2-methyl-4,5-benzindenyl)-2-(2-methyl-4-phenylindenyl)dibutylhafnium;

[0511]propylene-2-(2-ethyl-4,5-benzindenyl)-2-(2-methyl-4-phenylindenyl)dibutyltitanium;

[0512]propylene-2-(2-methyl-4,5-benzindenyl)-2-(2-ethyl-4-phenylindenyl)dibutylhafnium;

[0513]propylene-2-(2-ethyl-4,5-benzindenyl)-2-(2-ethyl-4-naphthylindenyl)dibutyltitanium;

[0514] propylene-2-(2-methylindenyl)-2-(4-phenylindenyl)dibutylhafnium;

[0515] propylene-2,2-bis(2-methyl-4-phenylindenyl)dibutyltitanium;

[0516] propylene-2,2-bis(2-ethyl-4-phenylindenyl)dibutylhafnium;

[0517]propylene-2,2-bis(2-methyl-4,6-diisopropylindenyl)dibutyltitanium;

[0518] propylene-2,2-bis(2-ethyl-4,6-diisopropylindenyl)dibutylhafnium;

[0519] propylene-2,2-bis(2-methyl-4-naphthylindenyl)dibutyltitanium;

[0520] propylene-2,2-bis(2-ethyl-4-naphthylindenyl)dibutyltitanium;

[0521]1,6-bis[methylsilylbis(2-methyl-4-phenylindenyl)dibutylhafnium]hexane;

[0522]1,6-bis[methylsilylbis(2-methyl-4,5-benzindenyl)dibutyltitanium]hexane;

[0523]1,6-bis[methylsilylbis(2-ethyl-4-phenylindenyl)dibutylhafnium]hexane;

[0524]1,6-bis[methylsilylbis(2-methyl-4-naphthylindenyl)dibutyltitanium]hexane;

[0525]1,6-bis[methylsilylbis(2-methyl-4,6,diisopropylindenyl)dibutylhafnium]hexane;

[0526]1,6-bis[methylsilyl(2-methyl-4-phenylindenyl)(4,5-benzindenyl)dibutyltitanium]hexane;

[0527]1-[methylsilylbis(tetrahydroindenyl)dibutylhafnium]-6-[ethylstannyl(cyclopentadienyl)(fluorenyl)dibutyltitanium]hexane;

[0528]1,6-disila-1,1,6,6-tetramethyl-1,6-bis[methylsiylbis(2-methyl-4-phenylindenyl)dibutylhafnium]hexane;

[0529]1,4-disila-1,4-bis[methylsilylbis(2-methyl-4-phenylindenyl)dibutylhafnium]cyclohexane;

[0530][1,4-bis(1-indenyl)-1,1,4,4-tetramethyl-1,4-disilabutane]bis(pentamethylcyclopentadienyldibutylhafnium);

[0531][1,4-bis(9-fluorenyl)-1,1,4,4-tetramethyl-1,4-disilabutane]bis(cyclopentadienyldibutylhafnium);

[0532][1,4-bis(1-indenyl)-1,1,4,4-tetramethyl-1,4-disilabutane]bis(cyclopentadienyldibutyltitanium);

[0533][1-(1-indenyl)-6-(2-phenyl-1-indenyl)-1,1,6,6-tetraethyl-1,6-disila-4-oxahexane]bis(tert-butylcyclopentadienyldibutyltitanium);

[0534][1,10-bis(2,3-dimethyl-1-indenyl)-1,1,10,10-tetramethyl-1,10-digermadecane]bis(2-methyl-4-phenylindenyldibutylhafnium);

[0535](1-methyl-3-tert-butylcyclopentadienyl)(1-phenyl-4-methoxy-7-chlorofluorenyl)dibutyltitanium;

[0536] (4,7-dichloroindenyl)(3,6-dimethylfluorenyl)dibutyltitanium;

[0537] bis(2,7-di-tert-butyl-9-cyclohexylfluorenyl)dibutylhafnium;

[0538](2,7-dimesitylfluorenyl)[2,7-bis(1-naphthyl)fluorenyl]dibutylhafnium;

[0539] dimethylsilylbis(fluorenyl)dibutyltitanium;

[0540] dibutylstannylbis(2-methylfluorenyl)dibutylhafnium;

[0541]1,1,2,2-tetraethyldisilanediyl(2-methylindenyl)(4-phenylfluorenyl)dibutyltitanium;

[0542] propylene-1-(2-indenyl)-2-(9-fluorenyl)dibutylhafnium;

[0543] 1,1-dimethyl-1-silaethylenebis(fluorenyl)dibutyltitanium;

[0544][4-(cyclopentadienyl)-4,7,7-trimethyl(tetrahydroindenyl)]dibutyltitanium;

[0545][4-(cyclopentadienyl)-4,7-dimethyl-7-phenyl(5,6-dimethyltetrahydroindenyl)]dibutylhafnium;

[0546][4-(cyclopentadienyl)-4,7-dimethyl-7-(1-naphthyl)(7-phenyltetrahydroindenyl)]dibutyltitanium;

[0547][4-(cyclopentadienyl)-4,7-dimethyl-7-butyl(6,6-diethyltetrahydroindenyl)]dibutylhafnium;

[0548][4-(3-tert-butylcyclopentadienyl)-4,7,7-trimethyl(tetrahydroindenyl)]dibutylhafnium;

[0549][4-(1-indenyl)-4,7,7-trimethyl(tetrahydroindenyl)]dibutyltitanium;

[0550] bis(indenyl)dichlorozirconium;

[0551] bis(fluorenyl)dichlorozirconium;

[0552] (indenyl)(fluorenyl)dichlorozirconium;

[0553] bis(cyclopentadienyl)dichlorotitanium;

[0554] (dimethylsilanediyl)bis(indenyl)dichlorozirconium;

[0555] (dimethylsilanediyl)bis(tetrahydroindenyl)dichlorozirconium;

[0556] (dimethylsilanediyl)(indenyl)dichlorozirconium;

[0557] (dimethylsilanediyl)bis(2-methylindenyl)dichlorozirconium;

[0558] (dimethylsilanediyl)bis(2-ethylindenyl)dichlorozirconium;

[0559](dimethylsilanediyl)bis(2-methyl-4,5-benzindenyl)dichlorozirconium;

[0560](dimethylsilanediyl)bis(2-ethyl-4,5-benzindenyl)dichlorozirconium;

[0561](dimethylsilanediyl)bis(2-methyl-4-phenylindenyl)dichlorozirconium;

[0562](dimethylsilanediyl)bis(2-ethyl-4-phenylindenyl)dichlorozirconium;

[0563](dimethylsilanediyl)bis(2-methyl-4,6-diisopropylindenyl)dichlorozirconium;

[0564] bis(cyclopentadienyl)(η⁴-butadiene)zirconium;

[0565] bis(methylcyclopentadienyl)(η⁴-butadiene)zirconium;

[0566] bis(n-butylcyclopentadienyl)(η⁴-butadiene)zirconium;

[0567] bisindenyl(η⁴-butadiene)zirconium;

[0568](tert-butylamido)dimethyl(tetramethyl-η⁵-cyclopentadienyl)silane(η⁴-butadiene)zirconium;

[0569] bis(2-methylbenzindenyl)(η⁴-butadiene)zirconium;

[0570] dimethylsilanediylbis(2-methyl-indenyl)(η⁴-butadiene)zirconium;

[0571] dimethylsilanediylbisindenyl(η⁴-butadiene)zirconium;

[0572] dimethylsilanediylbis(2-methylindenyl)(η⁴-butadiene)zirconium;

[0573]dimethylsilanediyl(2-methylbenzindenyl)(2-methyl-indenyl)(η⁴-butadiene)zirconium;

[0574]dimethylsilanediyl(2-methylbenzindenyl)(2-methyl-4-phenylindenyl)(η⁴-butadiene)zirconium;

[0575]dimethylsilanediyl(2-methylindenyl)(4-phenylindenyl)(η⁴-butadiene)zirconium;

[0576]dimethylsilanediylbis(2-methyl-4-phenylindenyl)(η⁴-butadiene)zirconium;

[0577]dimethylsilanediylbis(2-methyl-4,6-diisopropylindenyl)(η⁴-butadiene)zirconium;

[0578]dimethylsilanediylbis(2-methyl-4-naphthylindenyl)(η⁴-butadiene)zirconium;

[0579]isopropylidene(cyclopentadienyl)(fluorenyl)(η⁴-butadiene)zirconium;

[0580] isopropylidene(cyclopentadienyl)(indenyl)(η⁴-butadiene)zirconium;

[0581](4-η⁵-cyclopentadienyl)-4,7,7-triethyl-(η⁵-4,5,6,7-tetrahydroindenyl)(η⁴-butadiene)zirconium;

[0582] dimethylsilanediylbis(2-methyl-indenyl)(η⁴-butadiene)zirconium;

[0583] dimethylsilanediylbisindenyl(η⁴-butadiene)zirconium;

[0584]dimethylsilanediylbis(2-methylbenzindenyl)(η⁴-butadiene)zirconium;

[0585]dimethylsilanediyl(2-methylbenzindenyl)(2-methyl-indenyl)(η⁴-butadiene)zirconium

[0586]dimethylsilanediyl(2-methylbenzindenyl)(2-methyl-4-phenylindenyl)(η⁴-butadiene)zirconium;

[0587]dimethylsilanediyl(2-methylindenyl)(4-phenylindenyl)(η⁴-butadiene)zirconium;

[0588]dimethylsilanediylbis(2-methyl-4-phenylindenyl)(η⁴-butadiene)zirconium;

[0589]dimethylsilanediylbis(2-methyl-4,6-diisopropylindenyl)(η⁴-butadiene)zirconium;

[0590] dimethylsilanediylbis(2-methylindenyl)(η⁴-butadiene)zirconium;

[0591] dimethylsilanediylbisindenyl(η⁴-butadiene)zirconium;

[0592]dimethylsilanediylbis(2-methylbenzindenyl)(η⁴-butadiene)zirconium;

[0593]dimethylsilanediyl(2-methylbenzindenyl)(2-methylindenyl)(η⁴-butadiene)zirconium;

[0594]dimethylsilanediyl(2-methylbenzindenyl)(2-methyl-4-phenylindenyl)(η⁴-butadiene)zirconium;

[0595]dimethylsilanediyl(2-benzindenyl)(4-phenylindenyl)(η⁴-butadiene)zirconium;

[0596]dimethylsilanediylbis(2-methyl-4-phenylindenyl)(η⁴-butadiene)zirconium;

[0597]dimethylsilanediylbis(2-methyl-4,6-diisopropylindenyl)(η⁴-butadiene)zirconium;

[0598]dimethylsilanediylbis(2-methyl-4-naphthylindenyl)(η⁴-butadiene)zirconium;

[0599] dimethylsilanediylbis(2-methylindenyl)(η⁴-butadiene)zirconium;

[0600] dimethylsilanediylbisindenyl(η⁴-butadiene)zirconium;

[0601]dimethylsilanediylbis(2-methylbenzindenyl)(η⁴-butadiene)zirconium;

[0602]dimethylsilanediyl(2-methylbenzindenyl)(2-methylindenyl)(η⁴-butadiene)zirconium;

[0603]dimethylsilanediyl(2-methylbenzindenyl)(2-methyl-4-phenylindenyl)(η⁴-butadiene)zirconium;

[0604]dimethylsilanediyl(2-methylbenzindenyl)(4-phenylindenyl)(η⁴-butadiene)zirconium;

[0605]dimethylsilanediylbis(2-methyl-4-phenylindenyl)(η⁴-butadiene)zirconium;

[0606]dimethylsilanediylbis(2-methyl-4,6-diisopropylindenyl)(η⁴-butadiene)zirconium;

[0607]dimethylsilanediylbis(2-methyl-4-naphthylindenyl)(η⁴-butadiene)zirconium;

[0608]methylphenylmethylene(fluorenyl)(cyclopentadienyl)(η⁴-butadiene)zirconium;

[0609]diphenylmethylene(fluorenyl)(cyclopentadienyl)(η⁴-butadiene)zirconium;

[0610]isopropylidene(3-methylcyclopentadienyl)(fluorenyl)(η⁴-butadiene)zirconium;

[0611]dimethylsilanediyl(3-tert-butylcyclopentadienyl)(fluorenyl)(η⁴-butadiene)zirconium;

[0612]diphenylsilanediyl(3-(trimethylsilyl)cyclopentadienyl)(fluorenyl)(η⁴-butadiene)zirconium;

[0613]phenylmethylsilanediylbis(2-methylindenyl)(η⁴-butadiene)zirconium;

[0614] phenylmethylsilanediylbisindenyl(η⁴-butadiene)zirconium;

[0615]phenylmethylsilanediylbis(2-methyl-4,5-benzindenyl)(η⁴-butadiene)zirconium;

[0616]phenylmethylsilanediyl(2-methyl-4,5-benzindenyl)(2-methylindenyl)(η⁴-butadiene)zirconium;

[0617]phenylmethylsilanediyl(2-methyl-4,5-benzindenyl)(2-methyl-4-phenylindenyl)(η⁴-butadiene)zirconium;

[0618]phenylmethylsilanediyl(2-methylindenyl)(4-phenylindenyl)(η⁴-butadiene)zirconium;

[0619]phenylmethylsilanediylbis(2-methyl-4-phenylindenyl)(η⁴-butadiene)zirconium;

[0620]phenylmethylsilanediylbis(2-ethyl-4-phenylindenyl)(η⁴-butadiene)zirconium;

[0621]phenylmethylsilanediylbis(2-methyl-4,6-diisopropylindenyl)(η⁴-butadiene)zirconium

[0622]phenylmethylsilanediylbis(2-methyl-4-naphthylindenyl)(η⁴-butadiene)zirconium;

[0623] ethylenebis(2-methylindenyl)(η⁴-butadiene)zirconium;

[0624] ethylenebisindenyl(η⁴-butadiene)zirconium;

[0625] ethylenebis(2-methyl-4,5-benzindenyl)(η⁴-butadiene)zirconium;

[0626]ethylene(2-methyl-4,5-benzindenyl)(2-methyl-4-phenylindenyl)(η⁴-butadiene)zirconium;

[0627]ethylene(2-methylindenyl)(2-methyl-4-phenylindenyl)(η⁴-butadiene)zirconium;

[0628]ethylene(2-methylindenyl)(4-phenyl-indenyl)(η⁴-butadiene)zirconium;

[0629] ethylenebis(2-methyl-4,5-benzindenyl)(η⁴-butadiene)zirconium;

[0630] ethylenebis(2-methyl-4-phenylindenyl)(η⁴-butadiene)zirconium;

[0631]ethylenebis(2-methyl-4,6-diisopropylindenyl)(η⁴-butadiene)zirconium;

[0632] ethylenebis(2-methyl-4-naphthylindenyl)(η⁴-butadiene)zirconium;

[0633] ethylenebis(2-ethyl-4-phenylindenyl)(η⁴-butadiene)zirconium;

[0634]ethylenebis(2-ethyl-4,6-diisopropylindenyl)(η⁴-butadiene)zirconium;

[0635] ethylenebis(2-ethyl-4-naphthylindenyl)(η⁴-butadiene)zirconium;

[0636]dimethylsilanediylbis(2-ethyl-4-phenylindenyl)(η⁴-butadione)zirconium;

[0637]dimethylsilanediylbis(2,3,5-trimethylcyclopentadienyl)(η⁴-butadiene)zirconium;

[0638]1,6-{bis[methylsilylbis(2-methyl-4-phenylindenyl(η⁴-butadiene)zirconium)]hexane;

[0639]1,6-{bis[methylsilylbis(2-ethyl-4-phenylindenyl(η⁴-butadiene)zirconium)]hexane;

[0640]1,6-{bis[methylsilylbis(2-methyl-4-naphthylindenyl(η⁴-butadiene)zirconium)]hexane

[0641]1,6-{bis[methylsilylbis(2-methyl-4,5-benzindenyl(η⁴-butadiene)zirconium)]hexane;

[0642]1,6-{bis[methylsilyl(2-methyl-4-phenylindenyl)(2-methylindenyl)(η⁴-butadiene)zirconium)]hexane;

[0643]1,2-{bis[methylsilylbis(2-methyl-4-phenylindenyl(η⁴-butadiene)zirconium)]ethane;

[0644]1,2-{bis[methylsilylbis(2-ethyl-4-phenylindenyl(η⁴-butadiene)zirconium)]ethane;

[0645]1,2-{bis[methylsilylbis(2-methyl-4-naphthylindenyl(η⁴-butadiene)zirconium)]ethane

[0646]1,2-{bis[methylsilylbis(2-methyl-4,5-benzindenyl(η⁴-butadiene)zirconium)]ethane;

[0647]1,2-{bis[methylsilyl(2-methyl-4-phenylindenyl)(2-methylindenyl)(η⁴-butadiene)zirconium]}ethane.

EXAMPLES

[0648] Hereinafter the present invention will be described withreference to EXAMPLES but is not deemed to be limited to the followingEXAMPLES.

[0649] All of the reactions were carried out under a nitrogenatmosphere. THF, diethyl ether, hexane and benzene, which were used assolvents, were distilled to dehydration in a nitrogen flow in thepresence of sodium metal and benzophenone, and 1,2-dichloroethane wasused after distillation with phosphorus pentoxide under nitrogenpressure. Zirconocene dichloride was purchased from Aldrich ChemicalCompany, Inc. and Nichia Corporation and provided for use. The otherreagents were purchased from Kanto Kagaku, Tokyo Kasei Kogyo andAldrich. ¹H-NMR and ¹³C-NMR spectra were measured using Bruker ARX-400or JEOL JNM-LA300. In the measurements, the internal standard wastetramethylsilane for ¹H-NMR and deuterated chloroform for ¹³C-NMR. Gaschromatography was measured on SHIMADZU GC-14A gas chromatographequipped with SHIMADZU CBP1-M25-025 fused silica capillary column. Forrecording, SHIMADZU CR6A-Chromatopac integrator was employed. When theyield was determined by GC, mesitylene and n-dodecane were used as theinternal standard. As a packing material for the column chromatography,Kanto Kagaku Silica gel 60N (spherical, neutral) 40-100 micrometer wasused.

Reference Example 1

[0650] Dimethyl1,4,5,6,7,8-hexapropyl-9,10-dihydroanthracene-2,3-dicarboxylate

[0651] Bis(η⁵-cyclopentadienyl)dichlorozirconium (1.2 mmol) and THF (10ml) were charged in a Schlenk tube. This solution was cooled to −78° C.,and n-butyl lithium (2.4 mmols) was then added to the solution. Thesolution was stirred at −78° C. for an hour to givebis(η⁵-cyclopentadienyl)dibutylzirconium.

[0652] After 1,2-bis(2-hexynyl)-3,4,5,6-tetrapropylbenzene (1.0 mmol)was added to the reaction mixture at −78° C., the mixture was warmed toroom temperature and allowed to stand for an hour to give1-zirconacyclopenta-2,4-diene derivative.

[0653] To a solution of the thus obtained 1-zirconacyclopenta-2,4-diene(1.0 mmol) derivative in THF (10 ml), CuCl (2.0 mmols) and dimethylacetylenedicarboxylate (3.0 mmols) were added followed by stirring atroom temperature for an hour. Then, the reaction was quenched with 3Nhydrochloric acid. Next, the reaction mixture was extracted with diethylether, and washed with sodium hydrogencarbonate aqueous solution andbrine followed by drying over anhydrous magnesium sulfate. Afterconcentrating under reduced pressure, the residue was subjected tocolumn chromatography using silica gel as the packing material to givethe title compound.

[0654] The scheme for synthesis of the title compound of EXAMPLE 1 orsimilar compounds starting from the title compound of REFERENCE EXAMPLE2 or similar compounds, which were obtained by aromatizing the titlecompound of REFERENCE EXAMPLE 1 or similar compounds, is illustrated inFIG. 1.

Reference Example 2

[0655]

[0656] 15 Dimethyl 1,4,5,6,7,8-hexapropylanthracene-2,3-dicarboxylate

[0657] Dimethyl1,4,5,6,7,8-hexapropyl-9,10-dihydroanthracene-2,3-dicarboxylate obtainedin REFERENCE EXAMPLE 1 was used. 2,3-Dichloro-5,6-dicyanobenzo-quinone(0.729 g, 3.21 mmols) was added to a solution of dimethyl1,4,5,6,7,8-hexapropyl-9,10-dihydroanthracene-2,3-dicarboxylate (1.554g, 2.832 mmols) in benzene (25 ml). Subsequently, the mixture wasrefluxed for an hour. After filtration, the solvent in the mixture wasremoved in vacuum. Hexane was added to disintegrate into powders,whereby 1.393 g of the title compound was obtained as a white solid. Theisolation yield was 90%.

[0658]¹H NMR (CDCl₃, Me₄Si) δ1.13 (t, J=7.2 Hz, 6H), 1.14 (t, J=7.3 Hz,6H), 1.21 (t, J=7.3 Hz, 6H), 1.60-1.66 (m, 4H), 1.76-1.91 (m, 8H), 2.80(t, J=8.3 Hz 4H), 3.14-3.23 (m, 8H), 3.93 (s, 6H), 8.82 (s, 2H); ¹³C NMR(CDCl₃, Me₄Si) δ14.77 (2C), 15.01 (2C), 15.03 (2C), 24.61 (2C), 24.74(2C), 24.88 (2C), 31.69 (2C), 32.71 (2C), 32.81 (2C), 52.25 (2C), 121.42(2C), 126.48 (2C), 128.81 (2C), 130.52 (2C), 133.85 (2C), 137.50 (2C),137.90 (2C), 169.78 (2C). Elemental Analysis: Calcd. for C₃₆H₅₀: C,79.08; H, 9.22. Found: C, 79.02; H, 9.20. High resolution massspectrometer: Calcd. for C₃₈H₅₀O₄ 546.3709, Found: 546.3709.

Reference Example 3

[0659]

[0660] 2,3-Bis(hydroxymethyl)-1,4,5,6,7,8-hexapropylanthracene:

[0661] Dimethyl 1,4,5,6,7,8-hexapropylanthracene-2,3-dicarboxylateobtained in REFERENCE EXAMPLE 2 was used. After lithium aluminum hydridewas added to the solution of dimethyl1,4,5,6,7,8-hexapropylanthracene-2,3-dicarboxylate in diethyl ether at0° C., the mixture was warmed to room temperature and stirred for anhour. At room temperature, water was added to terminate the reaction.Next, the reaction mixture was rendered slightly acidic with 2N sulfuricacid and extracted with ether. After washing with brine, the extract wasdried over anhydrous magnesium sulfate. Column chromatography withsilica gel as the packing material was performed using hexane.Recrystallization from hexane gave 6.637 g (13.846 mmols) of the titlecompound as a light yellow solid. The isolation yield was 98%.

[0662]¹H NMR (CDCl₃, Me₄Si) δ1.11-1.26 (m,18H), 1.58-1.68 (m, 4H),1.74-1.81 (m, 8H), 2.78 (t, J=8.3 Hz, 4H), 3.15 (t, J=8.3 Hz, 4H), 3.26(t, J=8.3 Hz, 4H), 5.00 (s, 4H), 8.75 (s, 2H); ¹³C NMR (CDCl₃, Me₄Si)δ14.81 (2C), 15.05 (4C), 24.56 (2C), 24.94 (2C), 25.08 (2C), 31.37 (2C),31.75 (2C), 32.81 (2C), 60.18 (2C), 120.44 (2C), 129.30(2C), 129.74(2C), 133.03 (2C), 133.62 (2C), 136.42 (2C), 136.85 (2C). Elementalanalysis: Calcd. for C₃₄H₅₀O₂: C, 83.21; H, 10.27. Found: C, 83.00; H,10.50. High resolution mass spectrometer: Calcd. for C₃₄H₅₀O₂ 490.3811,Found: 490.3811.

Reference Example 4

[0663]

[0664] 2,3-Bis(bromomethyl)-1,4,5,6,7,8-hexapropylanthracene:

[0665] 2,3-Bis(hydroxymethyl)-1,4,5,6,7,8-hexapropylanthracene obtainedin REFERENCE EXAMPLE 3 was used. After phosphorus tribromide (1 eq.) wasadded to a solution of2,3-bis(hydroxymethyl)-1,4,5,6,7,8-hexapropylanthracene (1 eq.) inchloroform at room temperature, the mixture stirred at room temperaturefor an hour. Next, the reaction mixture was extracted with ether. Afterwashing with brine, the extract was dried over anhydrous magnesiumsulfate. The solvent was removed and the residue was recrystallized fromhexane to give 7.767 g (13.120 mmols) of the title compound as a lightyellow solid. The isolation yield was 96%.

[0666]¹H NMR (CDCl₃, Me₄Si) δ1.13 (t, J=7.3 Hz, 6H), 1.20 (t, J=7.2 Hz,6H), 1.24 (t, J=7.1 Hz, 6H), 1.60-1.66 (m, 4H), 1.75-1.87 (m, 8H), 2.78(t, J=84 Hz, 4H), 3.15 (t, J=8.3 Hz, 4H), 3.27 (t, J=8.3 Hz, 4H), 4.99(s, 4H), 8.72 (s, 2H); ¹³C NMR (CDCl₃, Me₄Si) δ14.96 (2C), 15.03 (4C),24.38 (2C), 24.60 (2C), 24.90 (2C), 29.91(2C), 31.63 (2C), 31.72 (2C),32.83 (2C), 120.69 (2C), 129.14 (2C), 129.17 (2C), 130.21 (2C), 133.76(2C), 137.43 (2C), 138.69 (2C). Elemental Analysis: Calcd. forC₃₄H₄₈Br₂: C, 66.23; H, 7.85; Br, 25.92. Found: C, 66.35; H, 7.92; Br,25.85.

Reference Example 5

[0667]

[0668] 2,3-Bis(2-hexynyl)-1,4,5,6,7,8-hexapropylanthracene:

[0669] 2,3-Bis(bromomethyl)-1,4,5,6,7,8-hexapropylanthracene obtained inREFERENCE EXAMPLE 4 was employed. N,N′-Dimethylproyleneurea (DMPU) and1-pentynyl lithium were added to the solution of2,3-bis(bromomethyl)-1,4,5,6,7,8-hexapropylanthracene in THF. Thereaction mixture was stirred at room temperature for an hour. Thereaction was quenched with 3N Hydrochloric acid. Next, the reactionmixture was extracted with ether. After washing with sodiumhydrogencarbonate aqueous solution and brine, the extract was dried overanhydrous magnesium sulfate. After the extract was concentrated underreduced pressure, column chromatography with silica gel as the packingmaterial was performed using hexane. Recrystallization from methanolgave 6.372 g (12.338 mmols) of the title compound as a yellow solid. Theisolation yield was 87%.

[0670]¹H NMR (CDCl₃, Me₄Si) δ0.93 (t, J=7.4 Hz, 6H), 1.12 (t, J=7.3 Hz,6H), 1.20 (t, J=7.3 Hz, 6H), 1.21 (t, J=7.4 Hz, 6H), 1.43-1.53 (m, 4H),1.58-1.66 (m,4H), 1.76-1.86 (m,8H), 2.11 (tt, J=2.1, 7.0 Hz, 4H), 2.77(t, J=8.3 Hz, 4H), 3.15 (t,J=8.2 Hz, 4H), 3.24 (t, J=8.3 Hz, 4H), 3.86(t, J=2.1 Hz, 4H), 8.69 (s, 2H); ¹³C NMR (CDCl₃, Me₄Si) δ13.47 (2C),14.97 (2C), 15.05 (4C), 20.11 (2C), 20.95 (2C), 22.38 (2C), 24.09 (2C),24.54 (2C), 24.96 (2C), 31.78 (2C), 31.90 (2C), 32.81 (2C), 78.57 (2C),80.99 (2C), 119.71 (2C), 129.19 (2C), 129.31 (2C), 131.17 (2C), 133.55(2C), 134.55 (2C), 136.20 (2C). Elemental Analysis: Calcd. for C₄₄H₆₂:C, 89.43; H, 10.57. Found: C, 89.17; H, 10.78.

Reference Example 6

[0671]

[0672] Dimethyl5,14-dihydro-1,4,6,8,9,10,11,13-octapropylpentacene-2,3-dicarboxylate

[0673] The reaction was carried out in a manner similar to REFERENCEEXAMPLE 1. Bis(η⁵-cyclopentadienyl)dichlorozirconium (1.2 mmol) and THF(10 ml) were charged in a Schlenk tube. This solution was cooled to −78°C., and n-butyl lithium (2.4 mmols) was then added to the solution. Thesolution was stirred at −78° C. for an hour to givebis(η⁵-cyclopentadienyl)dibutylzirconium.

[0674] At −78° C., 2,3-bis(2-hexynyl)-1,4,5,6,7,8-hexapropylanthracene(1.0 mmol) obtained in REFERENCE EXAMPLE 5 was added to the reactionmixture. The mixture was then warmed to room temperature and allowed tostand for an hour to give 1-zirconacyclopenta-2,4-diene derivative.

[0675] To a solution of the thus obtained 1-zirconacyclopenta-2,4-diene(1.0 mmol) derivative in THF (10 ml), CuCl (2.0 mmols) and dimethylacetylenedicarboxylate (3.0 mmols) were added followed by stirring atroom temperature for an hour. Then, 3N hydrochloric acid was added toterminate the reaction. Next, the reaction mixture was extracted withether, and washed with sodium hydrogencarbonate aqueous solution andbrine followed by drying over anhydrous magnesium sulfate. Afterconcentrating under reduced pressure, the residue was subjected to shortcolumn chromatography (elute, CHCl₃) using silica gel. Subsequentrecrystallization from a solvent mixture of chloroform and methanol gave5.528 g (10.782 mmols) of the title compound as a cream-like solid. Theisolation yield was 70%.

[0676]¹H NMR (CDCl₃, Me₄Si) δ1.11 (t, J=7.2 Hz, 6H), 1.13 (t, J=7.1Hz,6H), 1.22 (t, J=7.3 Hz, 6H), 1.23 (t, J=7.3 Hz, 6H), 1.61-1.73 (m, 8H),1.78-1.86 (m, 8H), 2.79 (t, J=8.3 Hz, 4H), 2.84 (t, J=8.2 Hz, 4H), 3.17(t, J=8.2 Hz, 4H), 3.32 (t,J=8.4 Hz, 4H), 3.85 (s, 6H), 4.11 (s, 4H),8.72 (s, 2H); ¹³C NMR (CDCl₃, Me₄Si) δ14.66 (2C), 14.93 (2C), 15.03(2C), 15.06 (2C), 24,31 (2C), 24.52 (2C), 24.60 (2C), 24.96 (2C), 30.39(2C), 31.30 (2C), 31.78 (2C), 32.80 (2C), 32.89 (2C), 52.18 (2C), 119.57(2C), 128.82 (2C), 129.17 (2C), 130.23 (2C), 131.12 (2C), 131.68 (2C),133.50 (2C), 135.11 (2C), 136.20 (2C), 139.80 (2C), 169.48 (2C).Elemental Analysis: Calcd. for C₅₀H₆₈O₄: C, 81.69; H, 9.46. Found: C,81.92; H, 9.35.

Example 1

[0677]

[0678] Dimethyl 1,4,6,8,9,10,11,13-octapropylpentacene-2,3-dicarboxylate

[0679] Chloranil (0.054 g, 0.22 mmol) was added to a solution ofdimethyl5,14-dihydro-1,4,6,8,9,10,11,13-octapropylpentacene-2,3-dicarboxylate(0.147 g, 0.2 mmol) obtained in REFERENCE EXAMPLE 6 in benzene (5 ml).The mixture was then refluxed for 24 hours. After concentration,chloroform was added to the residue followed by filtration. Afterconcentration, the concentrate was recrystallized from benzene to give0.048 g of the title compound as a blue solid. The isolation yield was33%.

[0680]¹H NMR (CDCl₃, Me₄Si) δ1.15 (t, J=7.2 Hz, 6H), 1.20 (t, J=7.3 Hz,6H), 1.27 (t, J=7.5 Hz, 6H), 1.29 (t, J=7.4 Hz, 6H), 1.62-1.68 (m, 4H),1.85-2.07 (m, 12H), 2.78 (t, J=7.5 Hz, 4H), 3.22-3.26 (m, 8H), 3.90 (bs,4H), 3.94 (s, 6H), 9.06 (s, 2H), 9.17 s, H); ¹³C NMR (CDCl₃, Me₄Si)δ14.85 (2C), 15.05 (2C), 15.13 (4C), 24.36 (2C), 24.60 (2C), 24.87 (2C),25.11 (2C), 31.33 (2C), 31.76 (2C), 32.67 (2C), 32.85 (2C), 52.26 (2C),120.08 (2C), 122.74 (2C), 126.23 (2C), 127.57 (2C), 127.76 (2C), 128.35(2C), 129.91 (2C), 133.37 (2C), 133.76 (2C), 136.77 (2C), 138.13 (2C),169.65 (2C). High resolution mass spectrometer: Calcd. for C₅₀H₆₆O₄730.4961, Found: 730.4995.

[0681] The scheme for synthesis of the title compound of EXAMPLE 1starting from the title compound of REFERENCE EXAMPLE 2, and via thetitle compound of REFERENCE EXAMPLE 5 obtained via the title compound ofREFERENCE EXAMPLE 3, then the title compound of REFERENCE EXAMPLE 4 andfurther via the title compound of REFERENCE EXAMPLE 6, is illustrated inFIG. 2.

Reference Example 7

[0682]

[0683] Dimethyl 1,4-dipropylnaphthalene-2,3-dicarboxylate

[0684] 2,3-Dichloro-5,6-dicyanobenzoquinone (1.362 g, 6.0 mmols) wasadded to a solution of dimethyl1,4-dipropyl-5,6,7,8-tetrahydronaphthalene-2,3-dicarboxylate (0.665 g,2.0 mmols) in benzene (20 ml). The mixture was then refluxed for 24hours. After filtration, the solvent in the mixture was removed invacuum. By column chromatography (ethyl acetate/hexane, 1/20) usingsilica gel, 0.464 g of the title compound was obtained as colorlesscrystals. The GC yield was 87% and the isolation yield was 71%.

[0685]¹H NMR (CDCl₃, Me₄Si) δ1.05 (t, J=7.4 Hz, 6H), 1.71-1.81 (m, 4H),3.07 (t, J=8.1 Hz, 4H), 3.91 (s, 6H), 7.60 (dd, J=3.4, 6.5 Hz, 2H), 8.12(dd, J=3.4, 6.5 Hz, 2H); ¹³C NMR (CDCl₃, Me₄Si) δ14.52 (2C), 24.64 (2C),32.20 (2C), 52.26 (2C), 125.53 (2C), 127.28 (2C), 128.25 (2C), 132.42(2C), 136.85 (2C), 169.53 (2C), Elemental Analysis: Calcd. for C₂₀H₂₄O₄:C,73.15; H, 7.37. Found: C, 73.10; H, 7.44.

Reference Example 8

[0686]

[0687] 2,3-Bis(hydroxymethyl)-1,4-dipropylnaphthalene

[0688] Dimethyl 1,4-dipropylnaphthlene obtained in REFERENCE EXAMPLE 7was treated with lithium aluminum hydride in a manner similar toREFERENCE EXAMPLE 3. Thus, 0.219 g (0.898 mmol) of the title compoundwas obtained as a white solid. Recrystallization from ether/hexane gavea small quantity of the title compound for elemental analysis. Theisolation yield was 90%.

[0689]¹H NMR (CDCl₃, Me₄Si) δ(t, J=7.3 Hz, 6H), 1.59-1.67 (m,4H), 3.08(t, J=8.2 Hz, 4H), 3.51 (bs, 2H), 4.87 (s,4H), 7.47 (dd, J=3.3, 6.5 Hz,2H), 8.04 (dd, J=3.3, 6.5Hz, 2H); ¹³C NMR (CDCl₃, Me₄Si) δ14.52 (2C),24.96 (2C), 31.52 (2C), 59.71 (2C), 125.05 (2C), 125.77 (2C), 132.12(2C), 134.53 (2C), 136.48 (2C). Elemental Analysis: Calcd. for C₁₈H₂₄O₂:C, 79.37; H, 8.88. Found: C, 79.43; H, 9.01.

Reference Example 9

[0690]

[0691] 2,3-Bis(bromomethyl)-1,4-dipropylnaphthalene

[0692] 2,3-Bis(hydroxymethyl)-1,4-dipropylnaphthalene obtained inREFERENCE EXAMPLE 8 was treated with phosphorus tribromide in a mannersimilar to REFERENCE EXAMPLE 4. By column chromatography (ethylacetate/hexane, 1/50) using silica gel, 0.115 g (0.4 mmol) of the titlecompound was obtained as a white solid. The isolation yield was 72%.

[0693]¹H NMR (CDCl₃, Me₄Si) δ1.14 (t, J=7.3 Hz, 6H), 1.75 (bs, 4H), 3.12(t, J=8.3 Hz, 4H), 4.92 (s, 4H), 7.49 (dd, J=3.3, 6.5 Hz, 2H), 8.02 (dd,J=3.3, 6.5 Hz, 2H); ¹³C NMR (CDCl₃, Me₄Si) δ14.77 (2C), 24.37 (2C),29.01 (2C), 31.11 (2C), 125.17 (2C), 126.59 (2C), 130.91 (2C), 132.44(2C), 138.44 (2C). Elemental Analysis: Calcd. for C₁₈H₂₂Br₂: C, 54.30;H, 5.57; Br, 40.13. Found: C, 54.21; H, 5.57; Br, 40.24.

Reference Example 10

[0694]

[0695] 2,3-Bis(2-hexynyl)-1,4-dipropylnaphthalene

[0696] 2,3-Bis(bromomethyl)-1,4-dipropylnaphthalene obtained inREFERENCE EXAMPLE 9 was treated with N,N′-dimethylpropyleneurea (DMPU)and 1-pentynyl lithium in a manner similar to REFERENCE EXAMPLE 5. Bycolumn chromatography (ethyl acetate/hexane, 1/50) using silica gel,1.661 g (4.787 mmols) of the title compound was obtained as a whitesolid. The isolation yield was 93%.

[0697] 1H NMR (CDCl₃, Me₄Si) δ0.91 (t, J=7.4 Hz, 6H), 1.12 (t, J=7.3 Hz,6H), 1.40-1.49 (m, 4H), 1.68-1.78 (m, 4H), 2.07 (tt, J=2.1, 7.0 Hz, 4H),3.10 (t, J=8.3 Hz, 4H), 3.84 (t, J=2.1 Hz, 4H), 7.41(dd, J=3.3, 6.5 Hz,2H), 8.01 (dd, J=3.3, 6.5 Hz, 2H); ¹³C NMR (CDCl₃, Me₄Si) δ13.43 (2C),14.77 (2C), 19.96 (2C), 20.88 (2C), 22.32 (2C), 24.11 (2C), 31.40 (2C),78.25 (2C), 80.95 (2C), 124.64 (2C) 125.02 (2C), 131.66 (2C), 132.48(2C), 134.99 (2C). Elemental Analysis: Calcd. for C₂₈H₃₆: C, 90.26; H,9.74. Found: C, 90.13; H, 9.86.

Reference Example 11

[0698]

[0699] Dimethyl5,12-dihydro-1,4,6,11-tetrapropylnaphthacene-2,3-dicarboxylate

[0700] 2,3-Bis(2-hexynyl)-1,4-dipropylnaphthalene obtained in REFERENCEEXAMPLE 10 was reacted with bis(η⁵-cyclopentadienyl)dibutylzirconium ina manner similar to REFERENCE EXAMPLE 1. Next, CuCl and dimethylacetylenedicarboxylate were added at room temperature to the reactionmixture as it was, followed by stirring for further 1 hour at roomtemperature. Thereafter, 3N hydrochloric acid was added to terminate thereaction. Next, the reaction mixture was extracted with ether, andwashed with sodium hydrogencarbonate aqueous is solution and brinefollowed by drying over anhydrous magnesium sulfate. After concentratingunder reduced pressure, the residue was subjected to columnchromatography (ethyl acetate/hexane, 1/10) using silica gel to give1.790 g (4.458 mmols) of the title compound as a light yellow solid. Theisolation yield was 78%. The X-ray crystal structure analysis of thetitle compound is shown in FIG. 3.

[0701]¹H NMR (CDCl₃, Me₄Si) δ1.09 (t, J=7.3 Hz, 6H), 1.16 (t, J=7.3 Hz,6H), 1.65-1.75 (m, 8H), 2.82 (t, J=8.2 Hz, 4H), 3.19 (t, J.=8.2 Hz, 4H),3.84 (s, 6H), 4.08 (s, 4H), 7.45 (dd, J=3.2, 6.6 Hz, 2H), 8.06 (dd,J=3.4, 6.5 Hz, 2H); ¹³C NMR (CDCl₃, Me₄Si) δ14.63 (2C), 14.76 (2C),24.27 (2C), 24.53 (2C), 30.21 (2C), 30.85 (2C), 32.85 (2C), 52.20 (2C),124.52 (2C), 124.86 (2C), 130.22 (2C), 131.07 (2C), 132.35 (2C), 132.39(2C), 135.12 (2C), 139.55 (2C), 169.44 (2C). Elemental Analysis: Calcd.for C₃₄H₄₂O₄: C, 79.34; H, 8.22. Found: C, 79.21; H, 8.36.

Example 2

[0702]

[0703] Dimethyl 1,4,6,11-tetrapropylnaphthacene-2,3-dicarboxylate

[0704] Dimethyl5,12-dihydro-1,4,6,11-tetrapropylnaphthacene-2,3-dicarboxylate obtainedin REFERENCE EXAMPLE 11 was used.

[0705] 2,3-Dichloro-5,6-dicyanobenzoquinone (0.050 g, 0.22 mmol) wasadded to a solution of dimethyl5,12-dihydro-1,4,6,11-tetrapropylnaphthacene-2,3-dicarboxylate (0.103 g,0.2 mmol) in 1,4-dioxane (5 ml). Subsequently, the mixture was refluxedfor 3 hours. After filtration, the solvent in the mixture was removed invacuum. Chloroform was added and the mixture was again filtered.Recrystallization from chloroform/methanol gave 0.076 g of the titlecompound as red needle-like crystals. The NMR yield was 97% and theisolated yield was 71%. The X-ray crystal structure analysis of thetitle compound is show in FIG. 4

[0706]¹H NMR (CDCl₃, Me₄Si) δ1.19 (t, J=7.3 Hz, 6H), 1.23 (t, J=7.3 Hz,6H), 1.92−1.86 (m, 8H), 3.26 (t, J=8.1 Hz, 4H), 3.72 (t, J=8.1 Hz, 4H),3.94 (s, 6H), 7.46 (dd, J=3.2, 7.0 Hz, 2H), 8.31 (dd, J=3.2, 7.0 Hz,2H), 9.19 (s, 2H); ¹³C NMR (CDCl₃, Me₄Si) δ14.81 (2C), 14.89 (2C), 24.67(2C), 24.89 (2C), 30.73 (2C) 32.72 (2C), 52.25 (2C), 122.65 (2C), 125.12(2C), 125.39 (2C), 126.67 (2C), 128.44 (2C), 128.77 (2C), 129.63 (2C),134.16 (2C), 137.87 (2C), 169.58 (2C). Elemental Analysis: Calcd. forC₃₄H₄₀O₄: C, 79.65; H, 7.86. Found: C, 79.43; H, 8.01. High resolutionmass spectrometer: Calcd. for C₃₄H₄₀O₄ 512.2937, Found: 512.2937.

[0707] The scheme for synthesis of the title compound of EXAMPLE 2starting from the title compound of REFERENCE EXAMPLE 7, and via thetitle compound of REFERENCE EXAMPLE 9 obtained via the title compound ofREFERENCE EXAMPLE 8, then via the title compound of REFERENCE EXAMPLE 10and further via the title compound of REFERENCE EXAMPLE 11, isillustrated in FIG. 5.

Reference Example 12

[0708]

[0709] 1,2,3,4,5,6,7,8-Octapropylanthracene

[0710] After 2,3-dichloro-5,6-dicyanoquinone (0.100 g, 0.440 mmol) wasadded to a solution of 1,2,3,4,5,6,7,8-octapropyl-9,10-dihydroanthracene(0.208 g, 0.400 mmol) in benzene (5 ml), the mixture was refluxed for anhour with heating. The reaction mixture was filtered to removehydroquinone and purified by silica gel column chromatography (ethylacetate/hexane, 99/1) to give the title compound (0.164 g) as a whitesolid. The isolation yield was 79%.

[0711]¹H NMR (CDCl₃, Me₄Si) δ1.11 (t, J=7.3 Hz, 12H), 1.20 (t, J=7.3 Hz,12H), 1.60-1.66 (m, 8H), 1.77-1.83 (m, 8H), 2.77 (t, J=7.7 Hz, 4H), 3.15(t, J=8.2 Hz, 8H), 8.66 (s, 2H); ¹³C NMR (CDCl₃, Me₄Si) δ15.06 (4C),15.09 (4C), 24.57 (4C), 25.02 (4C), 31.83 (4C), 32.83 (4C), 119.40 (2C),129.03 (4C), 133.47 (4C), 135.80 (4C).

[0712] Elemental Analysis: Calcd. for C₃₈H₅₈: C, 88.65; H, 11.35. Found:C, 88.76; H, 11.36.

[0713]2,3-Dichloro-5,6-dicyanoquinone (0.075 g, 0.440 mmol) was added toa solution of 1,2,3,4,5,6,7,8-octapropyl-9,10-dihydroanthracene (0.155g, 0.300 mmol) in benzene (5 ml) followed by stirring at roomtemperature for an hour. Analysis of the reaction solution by NMRrevealed that the products were 1,2,3,4,5,6,7,8-octapropylanthracene(NMR yield, 49%) and the Diels-Alder adduct (NMR yield, 30%), and 23% ofthe starting material remained.

Reference Example 13

[0714]

[0715] Dimethyl1,4,6,8,9,10,11,13-octaethyl-5,14-dihydropentacene-2,3-dicarboxylate

[0716] The title compound was obtained by the same manner as inREFERENCE EXAMPLES 2 to 6. In REFERENCE EXAMPLE 2, dimethyl1,4,5,6,7,8-hexapropyl-9,10-dihydroanthracene-2,3-dicarboxylate wasemployed, whereas dimethyl1,4,5,6,7,8-hexaethyl-9,10-dihydroanthracene-2,3-dicarboxylate wasemployed in REFERENCE EXAMPLE 13.

[0717] At the final step, 124 mg (0.50 mmol) of the title compound wasobtained as colorless single crystals by column chromatography(Et₂O/hexane, 1/10) using silica gel. The isolation yield was 40%. TheX-ray crystal structure analysis of the title compound is shown in FIG.6.

[0718]¹H NMR (CDCl₃, Me₄Si) δ1.27-1.36 (m, 12H), 1.41-1.48 (m, 12H),2.86-2.96 (m, 8H), 3.24-3.32 (m, 4H), 3.39-3.47 (m, 4H), 3.86 (s, 6H),4.18 (s,4H), 8.79 (s, 2H). ¹³C NMR (CDCl₃, Me₄Si) δ15.22, 15.49, 15.63,15.89, 21,87, 22.00, 22.99, 23.95, 29.95, 52.29, 119.49, 128.55, 128.99,130.12, 130.75, 133.11. 134.78, 136.43, 137.10, 139.66, 169.53. Highresolution mass spectrometer: Calcd. for C₄₂H₅₂O₄: 620.3866, Found:620.3869.

Reference Example 14

[0719]

[0720] Dimethyl 1,4,5,6,7,8-hexabutylanthracene-2,3-dicarboxylate

[0721] The reaction was carried out in a manner similar to REFERENCEEXAMPLE 2. In REFERENCE EXAMPLE 2, dimethyl1,4,5,6,7,8-hexapropyl-9,10-dihydroanthracene-2,3-dicarboxylate wasemployed, whereas dimethyl1,4,5,6,7,8-hexabutyl-9,10-dihydroanthracene-2,3-dicarboxylate wasemployed in REFERENCE EXAMPLE 14.

[0722] At the final step, 1764 mg (3 mmols) of the title compound wasobtained as a light yellow solid by column chromatography (Et₂O/hexane,1/10) using silica gel. The isolation yield was 93%.

[0723]¹H NMR (CDCl₃, Me₄Si) δ0.98-1.08 (m, 18H), 1.52-1.82 (m, 24H),2.78-2.85 (m, 4H), 3.16-3.26 (m, 8H), 3.92 (s, 6H), 8.84 (s, 2H). ¹³CNMR (CDCl₃, Me₄Si) δ13.94, 14.04, 14.1, 23.47, 23.59, 23.72, 29.13,30.16, 30.39, 33.56, 33.67, 52.30, 121.40, 126.41, 128.81, 130.55,133.91, 137.64, 137.94. High resolution mass spectrometer: Calcd. forC₄₂H₆₂O₄: 630.4648, Found: 630.4645.

Example 3

[0724]

[0725] Dimethyl 1,4,6,8,9,10,11,13-octaethylpentacene-2,3-dicarboxylate

[0726] The 1,4-dioxane solution of the compound obtained in REFERENCEEXAMPLE 13 was dehydrogenated with chloranil. By column chromatography(eluted first with Et₂O/hexane, 1/5 and then with 100% chloroform) usingsilica gel, 80 mg (0.5 mmol) of the title compound was obtained as adeep blue solid. The isolation yield was 26%.

[0727]¹H NMR (CDCl₃, Me₄Si) δ1.32 (t, J=7.4 Hz, 6H), 1.48-1.58 (m, 12H),1.66 (t, J=7.5 Hz, 6H), 2.90 (q, J=7.5 Hz, 4H), 3.33 (q, J=7.5 Hz, 8H),3.95 (s, 6H), 4.03 (q, J=7.5 Hz, 4H), 9.16 (s, 2H), 9.26 (s, 2H). ¹³CNMR (CDCl₃, Me4Si) δ15.36, 15.66, 15.79, 15.87,22.03,22.21,23.09,23.80,52.34, 119.92, 122.57, 126.05, 127.28, 127.47, 128.20,129.78, 134.66, 135.20, 137.69, 139.42, 169.69. High resolution massspectrometer: Calcd. for C₄₂H₅₀O₄: 618.3709, Found: 618.3680.

[0728] The foregoing results reveal that according to the process of thepresent invention, by introducing appropriate substituents on thecondensed polycyclic is aromatic compounds to improve the solubilitywhile the number of the rings is small, and proceeding furthersynthesis, the number of the polyacene rings can be increased, whilemaintaining the solubility.

[0729] Next, the relationship between substituents introduced andpolyacene derivatives obtained was examined by way of experiments, theresults of which are shown below.

Reference Example 15

[0730]1,2,3,4,5,6,7,8-Octapropylanthracene

[0731] After 2.2 equivalents of n-BuLi and 2.2 equivalents oftetramethylethylenediamine were added to the hexane solution of9,10-dihydro-1,2,3,4,5,6,7,8-octapropylanthracene at room temperature,the mixture was heated at 50° C. for 3 hours. The reaction solution wascooled to room temperature and 1.1 equivalent of methyl iodide was addedthereto. Stirring for an hour produced the title compound in the NMRyield of 98%. The compound was treated with 3N hydrochloric acid, andwashed with saturated sodium hydrogencarbonate aqueous solution andbrine. The organic phase was dried over anhydrous magnesium sulfate. Thesolvent was removed under reduced pressure to give the pure titlecompound in the yield of 96%. In this case, purification by columnchromatography, etc. was unnecessary.

[0732] Multi-substituted dihydroanthracenes were aromatized by similarexperimental procedures. The results are shown in TABLE 1. TABLE 1Dihydroanthracene Anthracene Yield (%)

98(96)

94(90)

96(92)

47(43)

[0733] In the table above, Yield denotes the yield by NMR and thenumeral within parenthesis denotes the yield when isolated.

[0734] As is evident also from TABLE 1, the system wherein the lithiumdopant and the lithium-removing reagent were used in combination wasextremely effective for the substituted polyhydropolyacenes, whereas theyield was 47% with the unsubstituted dihydroanthracene.

[0735] Next, various combinations of the lithium dopant and thelithium-removing reagent were examined by way of experiments, theresults of which are shown in TABLE 2. In the table, the lithium dopantand the lithium-removing reagent are designated as “RM” and “R′X”,respectively. TABLE 2 RM R′X Time/h Yield/% n-BuLi Mel 1 98 (96) Prl 2445 (40) BuBr 24 35 (31) sec-BuLi Mel 1 96 (92) tert-BuLi Mel 1 95 (92)MeLi Mel 1 40 (33) PhLi Mel 1 91 (86) EtMgBr Mel 1 N.R.

[0736] In the table, Yield denotes the yield by NMR and the numeralwithin parenthesis denotes the yield when isolated.

[0737] The results reveal that the yield was poor with PrI and BuBr, andgood with RM/MeI. Also, n-BuLi, sec-BuLi, tert-BuLi and PhLi can be usedas the lithium dopant.

[0738] The use of the lithium dopant in combination with thelithium-removing reagent provides some advantages, as compared toaromatization using Pd/C, trityl cations, n-BuLi/CdCl₂, or2,3-dichloro-5,6-dicyanoquinone. When using Pd/C, high temperatures suchas 200° C., 300° C., etc. are required, and with trityl cations, strongacids must be used and thus, it is likely to cause side reactions suchas rearrangement reaction, etc. To the contrary, with the combination ofthe lithium dopant and the lithium-removing reagent, the reactionproceeds under mild conditions. When using n-BuLi/CdCl₂, it is essentialto add toxic metal salts. In the aromatization by quinones such as2,3-dichloro-5,6-dicyanoquinone, chloranil, etc., multi-substitutedanthracenes involve the problem of causing Diels-Alder reaction asstated hereinabove to form by-products (the problem is improved bycontrolled reaction temperature and amount of quinones). However, thereaction of the present invention is free from such side reactions.

[0739] The combination of the lithium dopant and the lithium-removingreagent has the following characteristics. (1) No high reactiontemperature is required. (2) The reaction proceeds in a short period oftime and a good yield is obtained in aromatization of multi-substitutedpolyhydropolyacenes. (3) The product of high purity is obtained by asimple post-treatment.

Reference Example 16

[0740] The hydrocarbon condensed rings can be produced by the schemebelow. The hydrocarbon condensed rings can be further aromatized to givethe polyacenes.

[0741] (wherein (a) indicates the reaction with lithium aluminum hydrideat 0° C. followed by gradually elevating the temperature to roomtemperature; (b) indicates the reaction with phosphorus bromide at roomtemperature; (c) indicates the reaction with the alkynyl lithium shownby formula: R—CC—Li in THF solvent in the presence ofN,N′-dimethylpropyleneurea; and (d) indicates the reaction withbiscyclopentadienylzirconium dibutyl in THF solvent at −78° C. andfollowed by warming the system to room temperature, which is followed byreacting with dimethyl acetylenecarboxylate in the presence of CuCl).

Reference Example 17

[0742] The hydrocarbon condensed rings can be produced by the schemebelow. The hydrocarbon condensed rings can be further aromatized to givethe polyacenes.

[0743] (wherein (a) indicates the reaction with lithium aluminum hydrideat 0° C. followed by gradually elevating the temperature to roomtemperature; (b) indicates the reaction with phosphorus bromide at roomtemperature; (c) indicates the reaction with the alkynyl lithium shownby formula: R—CC—Li in THF solvent in the presence ofN,N′-dimethylpropyleneurea; and (d) indicates the reaction withbiscyclopentadienylzirconium dibutyl in THF solvent at −78° C. followedby warming the system to room temperature, which is followed by reactingwith dimethyl acetylenecarboxylate in the presence of CuCl).

Reference Example 18

[0744] The hydrocarbon condensed rings can be produced by the schemebelow. The hydrocarbon condensed rings can be further aromatized to givethe polyacenes.

[0745] (wherein (a) indicates the reaction with lithium aluminum hydrideat 0° C. followed by gradually elevating the temperature to roomtemperature; (b) indicates the reaction with phosphorus bromide at roomtemperature; (c) indicates the reaction with the alkynyl lithium shownby formula: R—CC—Li in THF solvent in the presence ofN,N′-dimethylpropyleneurea; and (d) indicates the reaction withbiscyclopentadienylzirconium dibutyl in THF solvent at −78° C. followedby warming the system to room temperature, which is followed by reactingwith dimethyl acetylenecarboxylate in the presence of CUCl).

Reference Example 19

[0746] The hydrocarbon condensed rings can be produced by the schemebelow. The hydrocarbon condensed rings can be further aromatized to givethe polyacenes.

[0747] (wherein (a) indicates the reaction with lithium aluminum hydrideat 0° C. followed by gradually elevating the temperature to roomtemperature; (b) indicates the reaction with phosphorus bromide at roomtemperature; (c) indicates the reaction with the alkynyl lithium shownby formula: R—CC—Li in THF solvent in the presence ofN,N′-dimethylpropyleneurea; and (d) indicates the reaction withbiscyclopentadienylzirconium dibutyl in THF solvent at −78° C. followedby warming the system to room temperature, Which is followed by reactingwith dimethyl acetylenecarboxylate in the presence of CuCl).

Reference Example 20

[0748] The hydrocarbon condensed rings can be produced by the schemebelow. The hydrocarbon condensed rings can be further aromatized to givethe polyacenes.

[0749] In this scheme, the following procedures were used. A solution ofCp₂ZrCl₂ (1.2 eq.) in THF was cooled to −78° C. on a dry ice-acetonebath, and a solution of n-BuLi (2.4 eq.) in hexane was added to thesolution. After the reaction solution was kept at −78° C. for an hour,the alkyne was added thereto followed by elevating to room temperature.The mixture was maintained at room temperature for 1 to 3 hours therebyto form zirconacyclopentadiene. 4-Octyne (1.5 eq.) anddibromobis(triphenylphosphine)nickel (II) (2.0 eq.) were added to theTHF solution of zirconacyclopentadiene (1.0 eq.) at room temperature.

[0750] After 24 hours, the mixture was treated with 3N hydrochloric acidand extracted with an appropriate solvent. The organic layers werecombined in one and washed with saturated sodium hydrogencarbonate andbrine followed by drying over magnesium sulfate. After the solvent wasremoved through an evaporator, the residue was suitably purified to givethe cyclized product.

[0751] 9,10-Dihydro-1,2,3,4,5,6,7,8-octapropylanthracene

[0752] Using the starting material (0.407 g, 1.00 mmol), the experimentwas performed by the procedures described above. Silica gel columnchromatography (ethyl acetate/hexane, 1/99) was conducted and the solidobtained was washed with ethanol to give9,10-dihydro-1,2,3,4,5,6,7,8-octapropylanthracene as white powders(0.251 g). The isolation yield was 48%.

[0753]¹H NMR (CDCl₃, Me₄Si) δ1.05 (t, J=7.3 Hz, 12H), 1.12 (t, J=7.3 Hz,12H), 1.47-1.61 (m, 16H), 2.54 (t, J=8.4 Hz, 8H), 2.70 (t, J=8.4 Hz,8H), 3.80 (s, 4H); ¹³C NMR (CDCl₃, Me₄Si) δ15.06 (4C), 15.12 (4C), 24.57(4C), 25.10 (4C), 29.90 (2C), 32.26 (4C), 32.31 (4C), 134.33 (4C),134.93 (4C), 136.30 (4C). Elemental Analysis: Calcd. for C₃₈H₆₀: C,88.30; H, 11.70. Found: C, 88.45; H, 11.67.

[0754] 1,2,3,4,6,8,9,10,11,13-Decapropyl-5,7,12,14-tetrahydropentacene

[0755] Using the starting material (1.19 g, 2.00 mmols), the experimentwas performed by the procedures described above. By recrystallizationfrom a solvent mixture of chloroform/methanol,1,2,3,4,6,8,9,10,11,13-decapropyl-5,7,12,14-tetrahydropentacene wasobtained as white powders (0.699 g). The isolation yield was 50%.

[0756]¹H NMR (CDCl₃, Me₄Si) δ1.03-1.18 (m, 30H), 1.51-1.59 (m, 20H),2.55 (t, J=7.8 Hz, 8H), 2.71 (t, J=7.7 Hz, 8H), 2.90 (t, J=7.7 Hz, 4H),3.87 (s, 8H); ¹³C NMR (CDCl₃, Me₄Si) δ14.98 (2C), 15.06 (4C), 15.08(4C), 24.29 (2C), 24.54 (4C), 25.11 (4C), 29.85 (4C), 31.93 (2C), 32.22(4C), 32.26 (4C), 133.06 (2C), 133.66 (4C), 133.95 (4C), 135.00 (4C),136.29 (4C). Elemental Analysis: Calcd. for C₅₂H₇₈: C, 88.82; H, 11.18.Found: C, 88.92; H, 11.37.

[0757] 5,7,8,9,10,12-Hexahydro-1,2,3,4,6,11-hexapropylnaphthacene

[0758] Using the starting material (0.456 g, 1.21 mmol), the experimentwas performed by the procedures described above. By silica gel columnchromatography (ethyl acetate/hexane, 1/99),5,7,8,9,10,12-hexahydro-1,2,3,4,6,11-hexapropylnaphthacene was obtainedas a white solid (0.283 g). The isolation yield was 48%.

[0759]¹H NMR (CDCl₃, Me₄Si) δ1.04 (t, J=7.3 Hz, 6H), 1.09-1.13 (m, 12H),1.47-1.58 (m, 12H), 1.76 (bs, 4H), 2.54 (t, J=8.2 Hz, 4H), 2.68-2.72 (m,8H), 2.75 (bs, 4H), 3.83 (s, 4H); ¹³C NMR (CDCl₃, Me₄Si) δ14.98 (2C),15.04 (2C), 15.07 (2C), 23.31 (2C), 23.41 (2C), 24.55 (2C), 25.11 (2C),27.31 (2C), 29.67 (2C), 31.37 (2C), 32.21 (2C), 32.26 (2C), 132.54 (2C),133.71 (2C), 134.11 (2C), 134.93 (4C), 136.23 (2C). Elemental Analysis:Calcd. for C₃₆H₅₄: C, 88.82; H, 11.18. Found: C, 88.68; H, 11.29.

Reference Example 21

[0760] The hydrocarbon condensed rings can be produced by the schemebelow.

[0761] The hydrocarbon condensed rings can be further aromatized to givethe polyacenes.

[0762] (wherein DMPU denotes N,N′-dimethylpropyleneurea.)

[0763] In this scheme, the following procedures were used. A solution ofCp₂ZrCl₂ (1.2 eq.) in THF was cooled to −78° C. on a dry ice-acetonebath, and a solution of n-BuLi (2.4 eq.) in hexane was added to thesolution. After the reaction solution was kept at −78° C. for an hour,the alkyne was added thereto followed by elevating to room temperature.The mixture was maintained at room temperature for 1 to 3 hours therebyto form zirconacyclopentadiene. Copper (I) chloride (2.1 eq.),N,N′-dimethylpropyleneurea (DMPU) (3.0 eq.) and diiodobenzene (1.0 eq.)were added to a THF solution of zirconacyclopentadiene (1.0 eq.) at roomtemperature. After stirring at 50° C. for 24 hours, the mixture wastreated with 3N hydrochloric acid. The mixture was extracted with anappropriate solvent, and the organic layers were combined in one, andthen washed with saturated sodium hydrogencarbonate and brine. Afterdrying over magnesium sulfate, the solvent was removed through anevaporator and the residue was suitably purified to give the couplingproduct.

[0764]5,12-Dihydro-1,2,3,4,6,11-hexapropylnaphthacene

[0765] Using the starting material (0.813 g, 2.00 mmols), the experimentwas performed by the procedures described above. By silica gel columnchromatography (ethyl acetate/hexane, 1/99),5,12-dihydro-1,2,3,4,6,11-hexapropyl-naphthacene was obtained as anorange solid (0.474 g). The isolation yield was 49%.

[0766]¹H NMR (CDCl₃, Me₄Si) δ1.14-1.19 (m, 18H), 1.48-1.79 (m, 12H),2.57 (t, J=8.4 Hz, 4H), 2.76 (t, J=8.4 Hz, 4H), 3.20 (t, J=8.3 Hz, 4H),4.04 (s, 4H) 7.42 (dd, J=3.3, 6.6 Hz, 2H), 8.05 (dd, J=3.3, 6.6 Hz, 2H);¹³C NMR (CDCl₃, Me₄Si) δ14.88 (2C), 15.06 (2C), 15.10 (2C), 24.29 (2C),24.69 (2C), 25.08 (2C), 30.42 (2C), 30.98 (2C), 32.26 (2C), 32.35 (2C),124.47 (4C), 131.03 (2C), 131.92 (2C), 134.11 (2C), 134.26 (2C), 135.03(2C), 136.57 (2C). High resolution mass spectrometer: Calcd. for C₃₆H₅₀482.3913, Found: 482.3902.

[0767] 1,2,3,4,6,8,13,15-Octapropyl-5,7,14,16-tetrahydrohexene

[0768] Using the starting material (0.296 g, 0.500 mmol), the experimentwas performed by the procedures described above. After hexane was addedand washing was thoroughly made, the mixture was filtered. Further bywashing with ethanol,1,2,3,4,6,8,13,15-octapropyl-5,7,14,16-tetrahydrohexene of high puritywas obtained as light orange powders (0.158 g). The isolation yield was47%.

[0769]¹H NMR (CDCl₃, Me₄Si) δ1.05 (t, J=7.3 Hz, 6H), 1.12-1.23 (m, 18H),1.48-1.79 (m, 16H), 2.56 (t, J=8.3 Hz, 4H), 2.72 (t, J=8.3 Hz, 4H), 2.97(t, J=8.3 Hz, 4H), 3.21 (t, J=8,2 Hz, 4H), 3.89 (s, 4H), 4.09 (s, 4H),7,41 (dd, J=3.3, 6.5 Hz, 2H), 8.05 (dd, J=3.3, 6.5 Hz, 2H); ¹³C NMR(CDCl₃, Me₄Si) δ14.87 (2C), 14.98 (2C), 15.08 (4C), 24.31 (2C), 24.46(2C), 24.58 (2C), 25.12 (2C), 29.93 (2C), 30.39 (2C), 30.96 (2C), 31.97(2C), 32.24 (2C), 32.29 (2C), 124.48 (4C), 131.03 (2C), 131.95 (2C),133.12 (2C), 133.73 (2C), 133.94 (2C), 134.02 (2C), 134.15 (2C), 135.02(2C), 136.36 (2C). Elemental Analysis: Calcd. for C₅₀H₆₈: C, 89.76; H,10.24. Found: C, 89.62; H, 10.30.

[0770] 1,2,3,4,6,13-Hexahydro-5,7,12,14-tetrapropylpentacene

[0771] Using the starting material (0.377 g, 1.0 mmol), the experimentwas performed by the procedures described above. By silica gel columnchromatography (ethyl acetate/hexane, 1/99),1,2,3,4,6,13-hexahydro-5,7,12,14-tetrapropylpentacene was obtained asorange needle-like crystals (0.085 g). The isolation yield was 19%.

[0772]¹HNMR (CDCl₃, Me₄Si) δ1.14 (t, J=7.3 Hz, 6H), 1.17 (t, J=7.5 Hz,6H), 1.56-1.62 (m, 4H), 1.71-1.77 (m, 8H), 2.74-2.78 (m, 8H), 3.19 (t,J=8.2 Hz, 4H), 4.06 (s, 4H), 7.41 (dd, J=3.2, 6.5 Hz, 2H), 8.05 (dd,J=3.2, 6.5 Hz, 2H); ¹³C NMR (CDCl₃, Me₄Si) δ14.88 (2C), 15.00 (2C),23.27 (2C), 23.56 (2C), 24.29 (2C), 27.37 (2C), 30.19 (2C), 30.94 (2C),31.37 (2C), 124.43 (2C), 124.49 (2C), 131.01 (2C), 131.94 (2C), 132.82(2C), 133.59 (2C), 134.17 (2C), 135.03 (2C). High resolution massspectrometer: Calcd. for C₃₄H₄₄ 452.3443, Found: 452.3437.

Reference Example 22

[0773] The hydrocarbon condensed rings can be produced by the schemebelow. The hydrocarbon condensed rings can be further aromatized to givethe polyacenes.

[0774] (wherein DMPU denotes N,N′-dimethylpropyleneurea).

[0775] In this scheme, the following procedures were used. A solution ofCp₂ZrCl₂ (2.4 eq.) in THF was cooled to −78° C. on a dry ice-acetonebath, and a solution of n-BuLi (4.8 eq.) in hexane was added to thesolution. After the reaction solution was kept at −78° C. for an hour,the alkyne was added thereto followed by elevating to room temperature.The mixture was maintained at room temperature for 1 to 3 hours therebyto form zirconacyclopentadiene. Copper (I) chloride (4.2 eq.),N,N′-dimethylpropyleneurea (DMPU) (6.0 eq.) and tetraiodobenzene (1.0eq.) were added to a THF solution of zirconacyclopentadiene (2.0 eq.) atroom temperature. After stirring at 50° C. for 24 hours, the mixture wastreated with 3N hydrochloric acid. The mixture was extracted with anappropriate solvent, and the organic layers were combined in one, andthen washed with saturated sodium hydrogencarbonate and brine. Afterdrying over magnesium sulfate, the solvent was removed through anevaporator and the residue was suitably purified to give the couplingproduct.

[0776]1,2,3,4,6,8,10,11,12,13,15,17-Dodecapropyl-5,9,14,18-tetrahydroheptacene

[0777] Using the starting material (0.606 g, 1.49 mmol), the experimentwas performed by the procedures described above. By recrystallizationfrom a solvent mixture of chloroform/methanol,1,2,3,4,6,8,10,11,12,13,15,17-dodecapropyl-5,9,14,18-tetrahydroheptacenewas obtained as light yellow powders (0.165 g). The isolation yield was25%.

[0778]¹H NMR (CDCl₃, Me₄Si) δ1.06 (t, J=7.2 Hz, 12H), 1.18 (t, J=7.2 Hz,12H), 1.25 (t, J=7.3 Hz, 12H), 1.50-1.67 (m, 16H), 1.83-1.89 (m, 8H),2.57 (t, J=8.4 Hz, 8H), 2.78 (t, J=8.3 Hz, 8H), 3.35 (t, J=7.9 Hz, 8H),4.09 (s, 8H), 8.76 (s, 2H),; ¹³C NMR (CDCl₃, Me₄Si) δ15.08 (8C), 15.11(4C), 24.33 (4C), 24.79 (4C), 25.10 (4C), 30.62 (4C), 31.45 (4C), 32.28(4C), 32.39 (4C), 119.50 (2C), 128.96 (4C), 131.21 (4C), 133.24 (4C),134.34 (4C), 135.02 (4C), 136.57 (4C). Elemental Analysis: Calcd. forC₆₆H₉₄: C, 89.32; H, 10.68. Found: C, 89.03; H, 10.62.

[0779]1,2,3,4,6,10,12.13,14,15,17,21-Dodecahydro-5,7,9,11,16,18,20,22-octapropylnonacene

[0780] Using the starting material (0.753 g, 2.0 mmols), the experimentwas performed by the procedures described above. After ether was addedand washing was thoroughly made, the mixture was filtered, and1,2,3,4,6,8,10,11,12,13,15,17-dodecapropyl-5,9,14,18-tetrahydroheptaceneof high purity was obtained as a light green solid (0.062 g). Theisolation yield was 7%.

[0781]¹H NMR (CDCl₃, Me₄Si) δ1.16 (t, J=7.2 Hz, 12H), 1.25 (t, J=7.2 Hz,12H), 1.58-1.64 (m, 8H), 1.78 (bs, 8H), 1.83-1.88 (m, 8H), 2.78-2.81 (m,16H), 3.35 (t, J=8.0 Hz, 8H), 4.11 (s, 8H), 8.76 (s, 2H); ¹³C NMR(CDCl₃, Me₄Si) δ14.99 (4C), 15.05 (4C), 23.31 (4C), 23.65(4C), 24.32(4C), 27.40 (4C), 30.40 (4C), 31.39 (4C), 119.47 (2C), 128.94 (4C),131.22 (4C), 132.84 (4C), 133.16 (4C), 133.82 (4C), 135.00 (4C). Highresolution mass spectrometer: Caled. for C₆₂H₈₂ 826.6412, Found:826.6389.

[0782] In the scheme described above, 2 equivalents ofzirconacyclopenta[b]tetrahydronaphthalene or 2 equivalents ofzirconacylopenta[b]hexahydroanthracene and 1 equivalent of1,2,4,5-tetraiodobenzene undergo coupling reaction. The ratio of thesereactants can be changed, and the coupling between 1 equivalent ofzirconacyclopenta[b]tetrahydronaphthalene or 1 equivalent ofzirconacylopenta[b]hexahydroanthracene and 1 equivalent of1,2,4,5-tetraiodobenzene can provide the hydrocarbon condensed ringswith iodine at the ortho-position of the terminal 6-membered ring.Alternatively, 2,3,6,7-tetraiodonaphthalene,2,3,6,7-tetraiodoanthracene, 2,3,8,9-tetraiodotetracene, etc. may beused, in place of 1,2,4,5-tetraiodobenzene. These hydrocarbon condensedrings can be further aromatized to give polyacenes.

Reference Example 23

[0783]

[0784] 9,10-Dipropyl-2,3-diiodo-5,6,7,8-tetrahydroanthracene

[0785] To a solution of bis(η⁵-cyclopentadienyl)dichlorozirconium (0.175g, 0.6 mmol) in THF (25 ml), n-butyl lithium (0.75 ml, 1.2 mmol, 1.6mol/l) was added at −78° C. After stirring the solution for an hour,4,10-tetradodecadiyne (0.095 ml, 0.5 mmol) was added to the solution. Acooling bath was withdrawn, and the mixture was stirred for an hour.Tetraiodobenzene (0.582 g, 1.0 mmol), DMPU (0.18 ml, 1.5 mmol) and CuCl(0.104 g, 1.1 mmol) were added to the mixture. After stirring at 50° C.for an hour, 3N hydrochloric acid was added to terminate the reaction.Next, the mixture was extracted with ether followed by washing withsodium hydrogencarbonate aqueous solution and brine. After concentratingunder reduced pressure, the residue was subjected to columnchromatography using silica gel as the packing material to give thetitle compound (0.148 g) as a colorless solid. The isolation yield was57%.

[0786]¹H NMR (CDCl₃, Me₄Si) δ1.07 (t, J=7.4 Hz, 6H), 1.51-1.63 (m, 4H),1.79-1.83 (m, 4H), 2.83-2.89 (m, 8H), 8.47 (s, 2H); ¹³C NMR (CDCl₃,Me₄Si) δ14.68 (2C), 22.80 (2C), 23.36 (2C), 27.81 (2C), 29.86 (2C),102.38 (2C), 131.58 (2C), 132.88 (2C), 135.16 (2C), 135.29 (2C). Highresolution mass spectrometer: Calcd. for C₂₀H₂₄I₂ 517.9968, Found:517.9963.

Reference Example 24

[0787]

[0788] 9,10-Dipropyl-2,3-diiodoanthracene

[0789] 9,10-Dipropyl-2,3-diiodo-5,6,7,8-tetrahydroanthracene (0.259 g,0.5 mmol), 2,3-dichloro-5,6-dicyanobenzoquinone (0.341 g, 1.5 mmol) and1,4-dioxane (3 ml) were charged in a reactor. Then, the mixture wasrefluxed for an hour. After cooling, the precipitates were removed byfiltration. The solvent in the mixture was removed in vacuum. Columnchromatography (hexane) was performed to give the title compound (0.109g) as a light yellow solid. The isolation yield was 42%.

[0790]¹H NMR (CDCl₃, Me₄Si) δ1.12 (t, J=7.4 Hz, 6H), 1.73-1.85 (m,4H),3.41 (t, J=8.1 Hz, 6H), 7.50 (dd, J=7.1, 6,6 Hz, 2H), 8.23 (dd, J=7.1,6.6 Hz, 2H), 8.79 (s, 2H); ¹³C NMR (CDCl₃, Me₄Si) δ14.67 (2C), 24.65(2C), 29.87 (2C), 103.11 (2C), 125.33 (2C), 125.69 (2C), 129.72 (2C),130.08 (2C), 133.19 (2C), 136.19 (2C).

[0791] High resolution mass spectrometer: Calcd. for C₂₀H₂₀I₂: 513.9655,Found: 513.9664.

Example 4

[0792]

[0793] 5,14-Bis(p-bromophenyl)-7,12-dipropyl-1,2,3,4-tetrahydropentacene

[0794] 1,8-Bis(p-bromophenyl)-1,7-octadiyne (0.191 g, 0.459 mmol) wasadded at −78° C. to a THF solution ofbis(η⁵-cyclopentadienyl)dibutylzirconium in THF, which was prepared frombis(η⁵-cyclopentadienyl)dichlorozirconium (0.161 g, 0.551 mmol) andn-butyl lithium (0.7 ml, 1.6 M, 1.1 mol/l). The mixture was then allowedto stand at room temperature for an hour. CuCl (0.095 g, 0.964 mmol),DMPU (0.17 ml, 1.38 mmol) and 2,3-diiodo-9,10-dipropylanthracene (0.236g, 0.459 mmol) were added to the mixture. After heating at 50° C. for anhour, the solvent in the mixture was removed in vacuum. Columnchromatography (chloroform) was performed. By recrystallization inchloroform/methanol, the title compound (0.177 g) was obtained as orangered. The isolation yield was 57%.

[0795]¹H NMR (CDCl₃, Me₄Si) δ0.93 (t, J=7.2 Hz, 6H), 1,60-1.76 (m, 8H),2.72 (bs, 4H), 3.33 (t, J=8.0 Hz, 4H), 7.29-7.35 (m, 6H), 7.74 (d, J=8.1Hz, 4H), 8.18 (dd, J=6.9, 3.3 Hz, 2H), 8.27 (s, 2H); ¹³C NMR (CDCl₃,Me₄Si) δ14.51 (2C), 22.83 (2C), 24.45 (2C), 29.30 (2C), 30.52 (2C),121.23 (2C), 122.16 (2C), 124.34 (2C), 125.27 (2C), 127.70 (2C), 128.67(2C), 129.78 (2C), 131.83 (4C), 132.13 (4C), 133.26 (2C), 133.66 (2C),135.74 (2C), 139.04 (2C).

Reference Example 25

[0796]

[0797] Dimethyl 3,4,5,6-tetrapropylphthalate

[0798] 4-Octyne (5.9 ml, 40.0 mmols) was added at −78° C. to a 70 ml THFsolution of bis(η⁵-cyclopentadienyl)dibutylzirconium, which was preparedfrom bis(η⁵-cyclopentadienyl)dichlorozirconium (7.016 g, 24.0 mmols) andn-butyl lithium (31.6 ml, 48.0 mmols, 1.52 M). After elevating to roomtemperature, the reaction mixture was stirred for an hour. DMAD(dimethyl acetylenedicarboxylate) (7.4 ml, 60.0 mmols) and CuCl (3.96 g,40.0 mmols) were added to the reaction mixture at room temperature.After stirring for an hour, 3N HCl was added for hydrolysis and themixture was extracted with hexane. Then, the extract was washed withsodium hydrogencarbonate aqueous solution and brine. After the extractwas dried over anhydrous magnesium sulfate, column chromatography wasperformed using silica gel as the packing material to give the titlecompound (4.917 g) as light yellow oil. The GC yield was 82% and theisolation yield was 74%.

[0799]¹H NMR (CDCl₃, Me₄Si) δ0.97 (t, J=7.2 Hz, 6H), 1.04 (t, J=7.3 Hz,6H), 1.45-1.57 (m, 8H), 2.56-2.62 (m, 8H), 3.83(s, 6H); ¹³C NMR (CDCl₃,Me₄Si), δ1468 (2C), 14.86 (2C), 24.60 (2C), 24.99 (2C), 31.70 (2C),32.59 (2C), 52.06 (2C), 130.34 (2C), 136.84 (2C), 142.11 (2C), 169.73(2C).

Reference Example 26

[0800]

[0801] 1,2-Bis(hydroxymethyl)-3,4,5,6-tetrapropylbenzene

[0802] Dimethyl 3,4,5,6-tetrapropylphthalate (5.22 g, 14.4 mmols) wasadded at 0° C. to a 50 ml THF solution of LiAlH₄ (1.20 g, 31.7 mmols).After stirring at room temperature for an hour, water was added forhydrolysis. The mixture was treated with 2N H₂SO₄ followed by extractionwith diethyl ether. Subsequently, the extract was washed with brine anddried over anhydrous magnesium sulfate. Column chromatography wasperformed using silica gel as the packing material to give the titlecompound (3.67 g) as a white solid. The isolation yield was 91%.

[0803]¹H NMR(CDCl₃, Me₄Si) δ1.05 (t, J=7.3 Hz, 6H), 1.05 (t, J=7.3 Hz,6H), 1.46-1.58 (m, 8H), 2.55 (t, J=8.4 Hz, 4H), 2.65 (t, J=8.4 Hz, 4H),3.27 (bs, 2H), 4.76 (s, 4H); ¹³C NMR (CDCl₃, Me₄Si) δ14.82 (2C), 15.04(2C), 24.75 (2C), 25.64 (2C), 31.90 (2C), 32.39 (2C), 59.82 (2C), 136.17(2C), 138.10 (2C), 139.58 (2C).

Reference Example 27

[0804]

[0805] 1,2-Bis(bromomethyl)-3,4,5,6-tetrapropylbenzene

[0806] Tribromophospnine (0.54 ml, 5.70 mmols) was dropwise added to 20ml of a chloroform solution of1,2-bis(hydroxymethyl)-3,4,5,6-tetrapropylbenzene (1.75 g, 5.70 mmols)at room temperature. After stirring for an hour, the mixture was treatedwith water followed by extracting with chloroform. Subsequently, theextract was washed with sodium hydrogencarbonate aqueous solution andbrine, followed by drying over anhydrous magnesium sulfate. Columnchromatography was performed using silica gel as the packing material togive the title compound (1.866 g) as a white solid. The GC yield was100% and the isolation yield was 87%.

[0807]¹H NMR (CDCl₃, Me₄Si) δ1.03-1.10 (m, 12H), 1.47-1.59 (m, 8H), 2.52(t, J=8.3 Hz, 4H), 2.66 (t, J=8.2 Hz, 4H), 4.71 (s, 4H); ¹³C NMR (CDCl₃,Me₄Si) δ14.99 (2C), 15.07 (2C), 24.67 (2C), 25.00 (2C), 29.04 (2C),31.85 (2C), 32.17 (2C), 132.70 (2C), 139.20 (2C), 141.00 (2C). ElementalAnalysis: Calcd. for C₂₀H₃₂Br₂: C, 55.57; H, 7.46; Br, 36.97. Found: C,55.46; H, 7.40; Br. 36.98.

Reference Example 28

[0808]

[0809] 1,2-Bis(2-hexynyl)-3,4,5,6-tetrapropylbenzene

[0810] n-Butyl lithium (9.7 ml, 15.56 mmols, 1.6 M) was added to a 30 mlTHF solution of 1-pentyne (1.67 ml, 17.12 mmols) at −78° C., and themixture was stirred at room temperature for an hour.1,2-Bis(bromomethyl)-3,4,5,6-tetrapropylbenzene (1.68 g, 3.89 mmols) andDMPU (1.9 ml, 15.56 mmols) were added to the mixture at roomtemperature. After stirring for an hour, 3N HCl was added to terminatethe reaction. The reaction mixture was extracted with hexane. Theextract was then washed with sodium hydrogencarbonate aqueous solutionand brine, followed by drying over anhydrous magnesium sulfate. Columnchromatography was performed using silica gel as the packing material togive the title compound (1.520 g) as a white solid. The GC yield was100% and the isolation yield was 97%

[0811]¹H NMR (CDCl₃, Me₄Si) δ0.93 (t, J=7.4 Hz, 6H), 1.05 (t, J=7.2 Hz,6H), 1.06 (t, J=7.2 Hz, 6H), 1.43-1.61 (m, 12H), 2.07 (tt, J=2.2, 7.1Hz, 4H), 2.51 (t, J=8.4 Hz, 4H), 2.61 (t, J=8.5 Hz, 4H), 3.59 (t, J=2.2Hz, 4H; ¹³C NMR (CDCl₃, Me₄Si) δ13.48 (2C), 15.03 (2C), 15.15 (2C),19.40 (2C), 20.99 (2C), 22.36 (2C), 24.46 (2C), 24.80 (2C), 32.33 (2C),32.41 (2C), 78.58 (2C), 80,34 (2C), 132.92 (2C), 137.21 (2C), 137.94(2C). Elemental Analysis: Calcd. for C₃₀H₄₆: C, 88.60; H, 11.40.

[0812] Found: C,88.49; H, 11.47. High resolution mass spectrometer:Calcd. for C₃₀ ₄₆ 406.3600, Found: 406.3626.

Reference Example 29

[0813]

[0814] 6,11-Dihydro-2,3-diiodo-5,7,8,9,10,12-hexapropylnaphthacene

[0815] n-Butyl lithium (3.0 ml, 4.8 mmols, 1.6mol/l) was added to a THFsolution (20 ml) of Cp₂ZrCl₂ (0.702 g, 2.4 mmols) at −78° C. After themixture was stirred for an hour,1,2-bis(2-hexynyl)-3,4,5,6-tetrapropylbenzene (0.813 g, 2.0 mmols) wasadded to the mixture. A cooling bath was withdrawn, and the mixture wasstirred for an hour. Tetraiodobenzene (1.16 g, 2.0 mmols), DMPU (0.73ml, 6.0 mmols) and CuCl (0.416 g, 4.2 mmols) were added to the mixture.After stirring for an hour at 50° C., 3N HCl was added to terminate thereaction. The reaction mixture was extracted with chloroform. Theextract was then washed with sodium hydrogencarbonate aqueous solutionand brine. After the pressure was reduced, column chromatography wasperformed using silica gel as the packing material to give the titlecompound (0.477 g) as a pink solid. The isolation yield was 33%

[0816]¹H NMR (CDCl₃, Me₄Si) δ1.06 (t, J=7.2 Hz, 6H), 1.15 (t, J=7.2 Hz,12H), 1.49-1.72 (m, 12H), 2.56 (t, J=8.4 Hz, 4H), 2.74 (t, J=8.4 Hz,4H), 3.07 (t, J=8.1 Hz, 4H), 3.98 (s, 4H), 8.52 (s, 2H); ¹³C NMR (CDCl₃,Me₄Si) δ14.78 (2C), 15.07 (2C), 15.13 (2C), 24.25 (2C), 24.68 (2C),25.04: (2C), 30.47. (2C), 30.59 (2C), 32.21 (2C), 32.34 (2C), 102.71(2C), 131.01 (2C), 131.97 (2C), 133.47 (2C), 135.09 (2C), 135.50 (2C),136.08 (2C), 136.84 (2C). High resolution mass spectrometer: Calcd. forC₃₆H₄₈I₂ 734.1846, Found: 734.1826.

Example 5

[0817]

[0818] 2,3-Diiodo-5,7,8,9,10,12-hexapropylnaphthacene

[0819] 6,11-Dihydro-5,7,8,9,10,12-hexapropyl-2,3-diiodonaphthacene (0.238 g, 0.324 mmol), 2,3-dichloro-5,6-dicyanobenzoquinone (0.081 g, 0.35mmol) and 1,4-dioxane (2 ml) were charged in a reactor. The mixture wasrefluxed for 3 hours. After cooling, the precipitates were removed byfiltration. The solvent in the mixture was removed in vacuum followed byrecrystallization from chloroform/methanol. The orange red titlecompound (0.081 g) was obtained. The isolation yield was 34%.

[0820]¹H NMR (CDCl₃, Me₄Si) δ1.13 (t, J=7.4 Hz, 6H), 1.21 (t, J=7.2 Hz,6H), 1.24 (t, J=7.2 Hz, 6H), 1.60-1.67 (m, 4H), 1.80-1.95 (m, 8H), 2.79(t, J=8.3 Hz, 4H), 3.19 (t, J=8.1 Hz, 4H), 3.60 (t, J=8.0 Hz, 4H), 8.82(s, 2H), 8.99 (s, 2H); ¹³C NMR (CDCl₃, Me₄Si) δ14.87 (2C), 15.02 (2C),15.09 (2C), 24.43 (2C), 24.82 (2C), 24.88 (2C), 30.49 (2C), 31.76 (2C),32.85 (2C), 102.09 (2C), 120.37 (2C), 127.87 (2C), 128.74 (2C), 130.13(2C), 133.01 (2C), 133.43 (2C), 136.37 (2C), 137.13 (2C).

[0821] High resolution mass spectrometer: Calcd. for C₃₆H₄₆I₂: 732.1689,Found: 732.1709.

Reference Example 30

[0822]

[0823] Dimethyl1,4-dipropyl-5,6,7,8-tetrahydronaphthalene-2,3-dicarboxylate

[0824] 4,10-Tetradodecadiyne (9.14 g, 48.03 mmols) was added at −78° C.to a 200 ml THF solution of bis(η⁵-cyclopentadienyl)dibutylzirconium,which was prepared from bis(η⁵-cyclopentadienyl)dichlorozirconium(16.849 g, 57.64 mmols) and n-butyl lithium (75.8 ml, 115.3 mmols, 1.52M). After elevating to room temperature, the reaction mixture wasstirred for an hour. DMAD (17.4 ml, 144.01 mmols) and CuCl (9.51 g,96.06 mmols) were added to the reaction mixture at room temperature.After stirring for an hour, 3N HCl was added for hydrolysis and themixture was extracted with hexane. The extract was then washed withsodium hydrogencarbonate aqueous solution and brine, followed by dryingover anhydrous magnesium sulfate. Column chromatography was performedusing silica gel as the packing material to give the title compound(8.133 g) as colorless crystals by recrystallization from methanol. TheGC yield was 58% and the isolation yield was 51%.

[0825]¹H NMR (CDCl₃, Me₄Si) δ0.96 (t, J=7.3 Hz, 6H), 1.50-1.56 (m, 4H),1.76 (bs, 4H), 2.59 (t, J=8.2 Hz, 4H), 2.74 (bs, 4H), 3.82 (s, 6H); ¹³CNMR (CDCl₃, Me₄Si) δ14.46 (2C), 22.41 (2C), 23.53 (2C). 26.80 (2C),31.96 (2C), 51.93 (2C), 129.56 (2C), 136.75 (2C), 138.41 (2C), 169.50(2C). Elemental Analysis: Calcd. for C₂₀H₂₈O₄: C, 72.26; H, 8.49. Found:C, 72.06; H, 8.60.

Reference Example 31

[0826]

[0827] Dimethyl 1,4-dipropylnaphthalene-2,3-dicarboxylate

[0828] 2,3-Dichloro-5,6-dicyanobenzoquinone (1.362 g, 6.0 mmols) wasadded to a solution of dimethyl1,4-dipropyl-5,6,7,8-tetrahydronaphthalene-2,3-dicarboxylate (0.665 g,2.0 mmols) in benzene (20 ml). The mixture was then refluxed for 24hours. After filtration, the solvent in the mixture was removed invacuum. Column chromatography was performed using silica gel as thepacking material to give the title compound (0.464 g ) as colorlesscrystals. The GC yield was 87% and the isolation yield was 71%.

[0829]¹H NMR (CDCl₃, Me₄Si) δ1.05 (t, J=7.4 Hz, 6H), 1.71-1.81 (m, 4H),3.07 (t, J=8.1 Hz, 4H), 3.91 (s, 6H), 7.60 (dd, J=3.4, 6,5 Hz, 2H), 8.12(dd, J=3.4, 6.5 Hz, 2H); ¹³C NMR (CDCl₃, Me₄Si) δ14.52 (2C), 24.64 (2C),32.20 (2C), 52.26 (2C), 125.53 (2C), 127.28 (2C), 128.25 (2C), 132.42(2C), 136.85 (2C), 169.53 (2C).

[0830] Elemental Analysis: Calcd. for C₂₀H₂₄O₄: C, 73.15; H,7.37. Found:C, 73.10; H, 7.44.

Reference Example 32

[0831]

[0832] 2,3-Bis(hydroxymethyl)-1,4-dipropylnaphthalene

[0833] Dimethyl 1,4-dipropylnaphthalene-2,3-dicarboxylate (0.295 g,0.898 mmol) was added to a 5 ml THF solution of LiAlH₄ (0.075 g, 1.98mmol) at 0° C. After stirring at room temperature for an hour, water wasadded to effect hydrolysis. The mixture was treated with 2N H₂SO₄followed by extraction with diethyl ether. The extract was washed withbrine and dried over anhydrous magnesium sulfate. The extract wasconcentrated under reduced pressure. The title compound (0.219 g) wasobtained as a white solid. The isolation yield was 90%.

[0834]¹H NMR (CDCl₃, Me₄Si) δ(t, J=7.3 Hz, 6H), 1.59-1.67 (m, 4H), 3.08(t, J=8.2 Hz, 4H), 3.51 (bs, 2H), 4.87 (s, 4H), 7.47 (dd, J=3.3, 6.5 Hz,2H), 8.04 (dd, J=3.3, 6.5 Hz, 2H); ¹³C NMR (CDCl₃, Me₄Si) δ14.52 (2C),24.96 (2C), 31.52 (2C), 59.71 (2C), 125.05 (2C), 125.77 (2C), 132.12(2C), 134.53 (2C), 136.48 (2C).

[0835] Elemental Analysis: Calcd. for C₁₈H₂₄O₂: C, 79.37; H, 8.88.Found: C, 79.43; H, 9.01.

Reference Example 33

[0836]

[0837] 2,3-Bis(bromomethyl)-1,4-dipropylnaphthalene

[0838] Tribromophospnine (0.04 ml, 0.42 mmol) was dropwise added to a 5ml chloroform solution of 2,3-bis(hydroxymethyl)-1,4-dipropylnaphthalene(0.109 g, 0.40 mmol) at room temperature. After stirring for an hour,the mixture was treated with water followed by extracting withchloroform. The extract was washed with sodium hydrogencarbonate aqueoussolution and brine, followed by drying over anhydrous magnesium sulfate.Column chromatography was performed using silica gel as the packingmaterial to give the title compound (0.115 g) as a white solid. Theisolation yield was 72%.

[0839]¹H NMR (CDCl₃, Me₄Si) δ1.14 (t, J=7.3 Hz, 6H), 1.75 (bs, 4H), 3.12(t, J=8.3 Hz, 4H), 4.92 (s, 4H), 7.49 (dd, J=3.3,6.5 Hz, 2H), 8.02 (dd,J=3.3, 6.5 Hz, 2H); ¹³C NMR (CDCl₃, Me₄Si) δ14.77 (2C), 24.37 (2C),29.01 (2C), 31.11(2c), 125.17 (2C), 126.59 (2C), 130.91 (2C), 132.44(2C), 138.44 (2C). Elemental Analysis:

[0840] Calcd. for C₁₈H₂₂Br₂: C, 54.30; H, 5.57; Br, 40.13, Found: C,54.21; H, 5.57; Br, 40.24.

Reference Example 34

[0841]

[0842] 2,3-Bis(2-hexynyl)-1,4-dipropylnaphthalene

[0843] n-Butyl lithium (7.6 ml, 19.1 mmols, 2.52 M) was added to a 30 mlTHF solution of 1-pentyne (2.05 ml, 21.06 mmols) at -78° C., and themixture was stirred at room temperature for an hour.2,3-Bis(bromomethyl)-1,4-dipropylnaphthalene (1.91 g, 4.79 mmols) andDMPU (2.3 ml, 19.1 mmols) were added to the mixture at room temperature.After stirring for an hour, the mixture was treated with 3N HCl andextracted with hexane. The extract was then washed with sodiumhydrogencarbonate aqueous solution and brine, followed by drying overanhydrous magnesium sulfate. Column chromatography was performed usingsilica gel as the packing material to give the title compound (1.66 g)as a white solid. The isolation yield was 93%

[0844]¹H NMR (CDCl₃, Me₄Si) 0.91 (t, J=7.4 Hz, 6H), 1.12 (t, J=7.3 Hz,6H), 1.40-1.49 (m, 4H), 1,68-1.78 (m, 4H), 2.07 (tt, J=2.1, 7.0 Hz, 4H),3.10 (t, J=8.3 Hz, 4H), 3.84 (t, J=2.1 Hz, 4H), 7.41 (dd, J=3,3, 6.5 Hz,2H), 8.01 (dd, J=3.3, 6.5 Hz, 2H); ¹³C NMR (CDCl₃, Me₄Si) δ13.43 (2C),14.77 (2C), 19.96 (2C), 20.88 (2C), 22.32 (2C), 24.11 (2C), 31.40 (2C),78.25 (2C), 80.95 (2C), 124.64 (2C), 125.02 (2C), 131.66 (2C), 132.48(2C), 134.99 (2C). Elemental Analysis: Calcd. for C₂₈H₃₆: C, 90.26; H,9.74. Found: C, 90.13; H, 9.86.

Reference Example 35

[0845]

[0846] 5,12-Dihydro-1,2,3,4,6,11-hexapropylnaphthacene

[0847] 2,3-Bis(2-hexynyl)-1,4-dipropylnaphthalene (0.373 g, 1.0 mmol)was added at −78° C. to a 20 ml THF solution ofbis(i⁵-cyclopentadienyl)dibutylzirconium, which was prepared frombis(η⁵-cyclopentadienyl)dichlorozirconium (0.351 g, 1.2 mmol) andn-butyl lithium (1.5 ml, 2.4 mmols, 1.6 M). After elevating to roomtemperature, the reaction mixture was stirred for an hour. 4-Octyne(0.22 ml, 1.5 mmol) and NiBr₂(PPh₃)₂ (0.892 g, 1.2 mmol) were added tothe reaction mixture at room temperature. After stirring for 24 hours,hydrolysis was effected by 3N HCl followed by extraction with hexane.The extract was washed with sodium hydrogencarbonate aqueous solutionand brine followed by drying over anhydrous magnesium sulfate. Columnchromatography was performed using silica gel as the packing material togive the title compound (0.224 g) as somewhat orange powders by flouredwith ethanol. The isolation yield was 46%.

[0848]¹H NMR (CDCl₃, Me₄Si) δ1.14-1.19 (m, 188H), 1.48-1.79 (m, 12H),2.57 (t, J=8.4 Hz, 4H), 2.76 (t, J=8.4 Hz, 4H), 3.20 (t, J=8.3 Hz, 4H),4.04 (s, 4H), 7.42 (dd, J=3.3, 6.6 Hz, 2H), 8.05 (dd, J=3.3, 6.6 Hz,2H); ¹³C NMR (CDCl₃, Me₄Si) δ14.88 (2C), 15.06 (2C), 15.10 (2C), 24.29(2C), 24.69 (2C), 25.08 (2C), 30.42 (2C), 30.98 (2C), 32.26 (2C), 32.35(2C). 124.47 (2C), 131.03 (2C), 131.92 (2C), 134.11 (2C), 134.26 (2C),135.03 (2C), 136.57 (2C). High resolution mass spectrometer: Calcd. forC₃₆H₅₀ 482.3913, Found: 482.3902.

Example 6

[0849]

[0850] 1,2,3,4,6,11-Hexapropylnaphthacene

[0851] 5,12-Dihydro-1,2,3,4,6,11-hexapropylnaphthacene (0.503 g, 1.04mmol), 2,3-dichloro-5,6-dicyanobenzoquinone (0.260 g, 1.14 mmol) and1,4-dioxane (3 ml) were charged in a reactor. The mixture was refluxedfor 24 hours. After cooling, the precipitates were removed byfiltration. The solvent in the mixture was removed in vacuum followed byrecrystallization from chloroform/methanol. The orange red titlecompound (0.112 g) was obtained. The NMR yield was 36% and the isolationyield was 22%.

[0852]¹H NMR (CDCl₃, Me₄Si) δ1.12 (t, J=7.3 Hz, 6H), 1.25 (t, J=7.4 Hz,6H), 1.27 (t, J=7.3 Hz, 6H), 1.63-1.69 (m, 4H), 1.85-2.01 (m, 8H), 2.80(t, J=8.4 Hz, 4H), 3.23 (t, J=8.3 Hz, 4H), 3.75 (t, J=8.1 Hz, 4H), 7.40(dd, J=7.1, 3.2 Hz, 2H), 8.30 (dd, J=7.1, 3.2Hz, 2H), 9.06 (s, 2H); ¹³CNMR (CDCl₃, Me₄Si) 14.99 (2C), 15.06 (2C), 15.14 (2C), 24.40 (2C), 24.76(2C), 24.91 (2C), 30.74 (2C), 31.81 (2C), 32.62 (2C), 32.83 (2C), 120.03(2C), 124.09 (2C), 125.35 (2C), 127.62 (2C), 128.55 (2C), 129.42 (2C),133.30 (2C), 133.36 (2C), 136.33 (2C). High resolution massspectrometer: Calcd. for C₃₆H₁₈: 480.3756, Found: 480.3747.

[0853] According to the present invention, the solubility of polyacenescan be improved by introducing substituents into the polyacenes on theside chains. Since various substituents can be introduced, the sidechains of polyacenes can be modified in various ways and their physicalproperties can be altered depending upon use.

[0854] Heretofore, there was a tendency that the solubility graduallydecreases as the number of aromatic rings in condensed polycyclicaromatic compounds increases. In the present invention, however, thesolubility can be maintained by introducing a variety of substituents,even if the number of aromatic rings in condensed polycyclic aromaticcompounds increases. Therefore, latitude in synthesis of variouscondensed polycyclic aromatic compounds can be markedly improved.

1. A polyacene derivative represented by general formula (I) below:

(wherein: each of R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹ and R¹⁰, which maybe the same or different, independently represents hydrogen atom; aC₁-C₄₀ hydrocarbon group which may optionally be substituted; a C₁-C₄₀alkoxy group which may optionally be substituted; a C₆-C₄₀ aryloxy groupwhich may optionally be substituted; an amino group which may optionallybe substituted; a hydroxy group; or a silyl group which may optionallybe substituted; provided that R⁶ and R⁷ may be cross-bridged with eachother to form a C₄-C₄₀ saturated or unsaturated ring, and the saturatedor unsaturated ring may be intervened by oxygen atom, sulfur atom or agroup shown by formula: —N(R¹¹)— (wherein R¹¹ is hydrogen atom or ahydrocarbon group), or may optionally be substituted; each of A¹ and A²,which may be the same or different, independently represents hydrogenatom; a halogen atom; a C₁-C₄₀ hydrocarbon group which may optionally besubstituted; a C₁-C₄₀ alkoxy group which may optionally be substituted;a C₆-C₄₀ aryloxy group which may optionally be substituted; a C₇-C₄₀alkylaryloxy group which may optionally be substituted; a C₂-C₄₀alkoxycarbonyl group which may optionally be substituted; a C₇-C₄₀aryloxycarbonyl group which may optionally be substituted; cyano group(—CN); carbamoyl group (—C(═O)NH₂); a haloformyl group (—C(═O)—X,wherein X represents a halogen atom); formyl group (—C(═O)—H); isocyanogroup; isocyanate group; thiocyanate group or thioisocyanate group;provided that A¹ and A² may be cross-bridged with each other to form aring shown by formula: —C(═O)—B—C(═O)— (wherein B is oxygen atom or agroup shown by formula —N(B¹)— (wherein B¹ is hydrogen atom, a C₁-C₄₀hydrocarbon group or a halogen atom)); n is an integer of not less than1; with proviso that, except for the case wherein R¹, R², R³, R⁴, R⁵,R⁶, R⁷, R⁸, R⁹, R¹⁰, A¹ and A² are all hydrogen atoms; when n is 1, atleast R¹, R², R⁴ and R⁹ are groups other than hydrogen atom, or at leastR³, R⁵, R⁸ and R¹⁰ are groups other than hydrogen atom; and, the casesof (a), (b), (c) and (d) below are excluded: (a) when R¹, R², R³, R⁴,R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, A¹ and A² are all methyl groups; (b) when R³,R⁴, R⁹ and R¹⁰ are all aryl groups that may optionally be substituted;(c) when R¹, R², R⁴ and R⁹ are all alkoxy or aryloxy groups, and R³, R⁵,R⁶, R⁷, R⁸, R¹⁰, A¹ and A² are all hydrogen atoms; (d) when R³, R⁵, R⁸and R¹⁰ are all alkoxy or aryloxy groups, and R¹, R², R⁴, R⁶, R⁷, R⁹, A¹and A² are all hydrogen atoms; and, when n is 2, the cases of (a′),(b′), (c′) and (d′) below are excluded: (a′) a pentacene derivativerepresented by formula (Ia) below:

wherein R¹, R², R³, R⁴, R^(5a), R^(5b), R⁶, R⁷, R^(8a), R^(8b), R⁹, R¹⁰,A¹ and A² are all methyl groups; or R¹, R², R³, R⁴, R^(5a), R^(5b),R^(8a), R^(8b), R⁹ and R¹⁰ are all hydrogen atoms and at least one ofR⁶, R⁷, A¹ and A² is an aryl group; or at least one of R¹, R², R³, R⁴,R^(5a), R^(5b), R⁶, R⁷, R^(8a), R^(8b), R⁹, R¹⁰, A¹ and A² is adiarylamine group; (b′) a pentacene derivative represented by formula(Ib) below:

wherein R¹, R², R^(5b) and R^(8b) are all alkoxy or aryloxy groups; (c′)a pentacene derivative represented by formula (Ic) below:

wherein at least 2 of R³, R^(5a), R^(8a) and R¹⁰ are aryl or arylalkynylgroups; or at least one of R³, R^(5a), R^(8a) and R¹⁰ is an arylalkenylgroup; or R³, R^(5a), R^(8a) and R¹⁰ are all alkoxy or aryloxy groups;(d′) a pentacene derivative represented by formula (Id) below:

wherein R⁴ and R⁹ are hydrogen atom, a hydrocarbon group, an alkoxygroup, an aryloxy group, a halogen atom or hydroxy group.
 2. Thepolyacene derivative according to claim 1, wherein at least 5 of R¹, R²,R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, A¹ and A² are groups other thanhydrogen atom.
 3. The polyacene derivative according to claim 1, whereinat least 6 of R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, A¹ and A² aregroups other than hydrogen atom.
 4. The polyacene derivative accordingto claim 1, wherein the polyacene derivative is a pentacene derivativerepresented by formula (Ia):

(wherein: each of R¹, R², R³, R⁴, R^(5a), R^(5b), R⁶, R⁷, R^(8a),R^(8b), R⁹ and R¹⁰, which may be the same or different, independentlyrepresents hydrogen atom; a C₁-C₄₀ hydrocarbon group which mayoptionally be substituted; a C₁-C₄₀ alkoxy group which may optionally besubstituted; a C₆-C₄₀ aryloxy group which may optionally be substituted;an amino group which may optionally be substituted; a hydroxy group; ora silyl group which may optionally be substituted; provided that R⁶ andR⁷ may be cross-bridged with each other to form a C₄-C₄₀ saturated orunsaturated ring, and the saturated or unsaturated ring may beintervened by oxygen atom, sulfur atom or a group shown by formula:—N(R¹¹)— (wherein R¹¹ is hydrogen atom or a hydrocarbon group), or mayoptionally be substituted; each of A¹ and A², which may be the same ordifferent, independently represents hydrogen atom; a halogen atom; aC₁-C₄₀ hydrocarbon group which may optionally be substituted; a C₁-C₄₀alkoxy group which may optionally be substituted; a C₆-C₄₀ aryloxy groupwhich may optionally be substituted; a C₇-C₄₀ alkylaryloxy group whichmay optionally be substituted; a C₂-C₄₀ alkoxycarbonyl group which mayoptionally be substituted; a C₇-C₄₀ aryloxycarbonyl group which mayoptionally be substituted; cyano group (—CN); carbamoyl group(—C(═O)NH₂); a haloformyl group (—C(═O)—X, wherein X represents ahalogen atom); formyl group (—C(═O)—H); isocyano group; isocyanategroup; thiocyanate group or thioisocyanate group; provided that A¹ andA² may be cross-bridged with each other to form a ring shown by formula:—C(═O)—B—C(═O)— (wherein B is oxygen atom or a group shown by formula—N(B¹)— (wherein B¹ is hydrogen atom, a C₁-C₄₀ hydrocarbon group or ahalogen atom))), and, at least 5 of R¹, R², R³, R⁴, R^(5a), R^(5b), R⁶,R⁷, R^(8a), R^(8b), R⁹, R¹⁰, A¹ and A² are groups other than hydrogenatom.
 5. The polyacene derivative according to claim 4, wherein at least6 of R¹, R², R³, R⁴, R^(5a), R^(5b), R⁶, R⁷, R^(8a), R^(8b), R⁹, R¹⁰, A¹and A² are groups other than hydrogen atom.
 6. The polyacene derivativeaccording to claim 4, wherein at least 7 of R¹, R², R³, R⁴, R^(5a),R^(5b), R⁶, R⁷, R^(8a), R^(8b), R⁹, R¹⁰, A¹ and A² are groups other thanhydrogen atom.
 7. The polyacene derivative according to claim 4, whereinat least 8 of R¹, R², R³, R⁴, R^(5a), R^(5b), R⁶, R⁷, R^(8a), R^(8b),R⁹, R¹⁰, A¹ and A² are groups other than hydrogen atom.
 8. The polyacenederivative according to claim 4, wherein at least 9 of R¹, R², R³, R⁴,R^(5a), R^(5b), R⁶, R⁷, R^(8a), R^(8b), R⁹, R¹⁰, A¹ and A² are groupsother than hydrogen atom.
 9. The polyacene derivative according to claim4, wherein at least 10 of R¹, R², R³, R⁴, R^(5a), R^(5b), R⁶, R⁷,R^(8a), R^(8b), R⁹, R¹⁰, A¹ and A² are groups other than hydrogen atom.10. The polyacene derivative according to any one of claims 1 through 3wherein any one of the combinations of R¹ and R², R³ and R¹⁰, R⁴ and R⁹,R⁵ and R⁸, R⁶ and R⁷, and A¹ and A² are the same substituents.
 11. Thepolyacene derivative according to any one of claims 4 through 9, whereinany one of the combinations of R¹ and R², R³ and R¹⁰, R⁴ and R⁹, R^(5a)and R^(8a), R^(5b) and R^(8b), R⁶ and R⁷, and A¹ and A² are the samesubstituents.
 12. The polyacene derivative according to any one ofclaims 1 through 3, wherein any one of R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸,R⁹ and R¹⁰ is a C₁-C₄₀ hydrocarbon group which may optionally besubstituted, a C₁-C₄₀ alkoxy group which may optionally be substituted,or a C₆-C₄₀ aryloxy group which may optionally be substituted.
 13. Thepolyacene derivative according to any one of claims 4 through 9, whereinany one of R¹, R², R³, R⁴, R^(5a), R^(5b), R⁶, R⁷, R^(8a), R^(8b), R⁹and R¹⁰ is a C₁-C₄₀ hydrocarbon group which may optionally besubstituted, a C₁-C₄₀ alkoxy group which may optionally be substituted,or a C₆-C₄₀ aryloxy group, which may optionally be substituted.
 14. Thepolyacene derivative according to claim 1, wherein when n is 1, A¹ andA² are an alkoxycarbonyl group, and R¹, R², R⁴ and R⁹ are an alkyl oraryl group.
 15. The polyacene derivative according to claim 1, whereinwhen n is 1, A¹, A², R¹, R², R⁴ and R⁹ are an alkyl or aryl group. 16.The polyacene derivative according to claim 1, wherein when n is 1, A¹and A² are a halogen atom and R³, R⁵, R⁶, R⁷, R⁸ and R¹⁰ are an alkyl oraryl group.
 17. The polyacene derivative according to claim 4, whereinwhen the polyacene derivative is the pentacene derivative represented bythe formula (Ia) above, A¹ and A² are an alkoxycarbonyl group and R¹,R², R⁴, R^(5b), R⁶, R⁷, R^(8b)and R⁹ are an alkyl or aryl group.
 18. Thepolyacene derivative according to claim 4, wherein when the polyacenederivative is the pentacene derivative represented by the formula (Ia)above, A¹, A², R¹, R², R⁴, R^(5b), R⁶, R⁷, R^(8b) and R⁹ are an alkyl oraryl group.
 19. The polyacene derivative according to claim 4, whereinwhen the polyacene derivative is the pentacene derivative represented bythe formula (Ia) above, A¹ and A² are a halogen group and R³, R^(5a),R^(8a) and R¹⁰ are an alkyl or aryl group.
 20. A process of producingthe polyacene derivative represented by formula (I) below:

(wherein: each of R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹ and R¹⁰, which maybe the same or different, independently represents hydrogen atom; aC₁-C₄₀ hydrocarbon group which may optionally be substituted; a C₁-C₄₀alkoxy group which may optionally be substituted; a C₆-C₄₀ aryloxy groupwhich may optionally be substituted; an amino group which may optionallybe substituted; a hydroxy group; or a silyl group which may optionallybe substituted; provided that R⁶ and R⁷ may be cross-bridged with eachother to form a C₄-C₄₀ saturated or unsaturated ring, and the saturatedor unsaturated ring may be intervened by oxygen atom, sulfur atom or agroup shown by formula: —N(R¹¹)— (wherein R ¹¹ is hydrogen atom or ahydrocarbon group), or may optionally be substituted; each of A¹ and A²,which may be the same or different, independently represents hydrogenatom; a halogen atom; a C₁-C₄₀ hydrocarbon group which may optionally besubstituted; a C₁-C₄₀ alkoxy group which may optionally be substituted;a C₆-C₄₀ aryloxy group which may optionally be substituted; a C₇-C₄₀alkylaryloxy group which may optionally be substituted; a C₂-C₄₀alkoxycarbonyl group which may optionally be substituted; a C₇-C₄₀aryloxycarbonyl group which may optionally be substituted; cyano group(—CN); carbamoyl group (—C(═O)NH₂); a haloformyl group (—C(═O)—X,wherein X represents a halogen atom); formyl group (—C(═O)—H); isocyanogroup; isocyanate group; thiocyanate group or thioisocyanate group;provided that A¹ and A² may be cross-bridged with each other to form aring shown by formula: —C(═O)—B—C(═O)— (wherein B is oxygen atom or agroup shown by formula —N(B¹)— (wherein B¹ is hydrogen atom, a C₁-C₄₀hydrocarbon group or a halogen atom)); and, n is an integer of not lessthan 1), which comprises aromatizing hydrocarbon condensed ringsrepresented by formula (II) below:

(wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, A¹, A² and n have thesame significance as defined above; the bond shown by formula belowrepresents a single bond or a double bond;

provided that when the bond is a single bond, hydrogen atom is furtherbound directly to the carbon atoms which are directly bound to R⁵, R⁶,R⁷ and R⁸); in the presence of a dehydrogenation reagent.
 21. Theprocess of producing the polyacene derivative according to claim 20,wherein the dehydrogenation reagent is a combination of a lithium dopantand a lithium-removing reagent, and the lithium dopant is first added tothe hydrocarbon condensed rings followed by adding the lithium-removingreagent.
 22. The process of producing the polyacene derivative accordingto claim 21, wherein the lithium dopant is an alkyl lithium and thelithium-removing reagent is an alkyl halide.
 23. The process ofproducing the polyacene derivative according to claim 20, wherein thedehydrogenation reagent is a compound represented by formula (III):

(wherein each of X¹, X², X³ and X⁴, which may be the same or different,independently represents a halogen atom or cyano group).
 24. The processof producing the polyacene derivative according to claim 20, wherein thedehydrogenation reagent contains palladium.
 25. The process of producingthe polyacene derivative according to any one of claims 20 through 24,wherein at least 5 of R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, A¹ and A²are groups other than hydrogen atom.
 26. The process of producing thepolyacene derivative according to any one of claims 20 through 24,wherein at least 6 of R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, A¹ and A²are groups other than hydrogen atom.
 27. The process of producing thepolyacene derivative according to any one of claims 20 through 24,wherein the polyacene derivative is a pentacene derivative representedby formula (Ia):

(wherein: each of R¹, R², R³, R⁴, R^(5a),R^(5b), R⁶, R⁷, R^(8a), R^(8b),R⁹ and R¹⁰, which may be the same or different, independently representshydrogen atom; a C₁-C₄₀ hydrocarbon group which may optionally besubstituted; a C₁-C₄₀ alkoxy group which may optionally be substituted;a C₆-C₄₀ aryloxy group which may optionally be substituted; an aminogroup which may optionally be substituted; a hydroxy group; or a silylgroup which may optionally be substituted; provided that R⁶ and R⁷ maybe cross-bridged with each other to form a C₄-C₄₀ saturated orunsaturated ring, and the saturated or unsaturated ring may beintervened by oxygen atom, sulfur atom or a group shown by formula:—N(R¹¹)— (wherein R¹¹ is hydrogen atom or a hydrocarbon group), or mayoptionally be substituted; each of A¹ and A², which may be the same ordifferent, independently represents hydrogen atom; a halogen atom; aC₁-C₄₀ hydrocarbon group which may optionally be substituted; a C₁-C₄₀alkoxy group which may optionally be substituted; a C₆-C₄₀ aryloxy groupwhich may optionally be substituted; a C₇-C₄₀ alkylaryloxy group whichmay optionally be substituted; a C₂-C₄₀ alkoxycarbonyl group which mayoptionally be substituted; a C₇-C₄₀ aryloxycarbonyl group which mayoptionally be substituted; cyano group (—CN); carbamoyl group(—C(═O)NH₂); a haloformyl group (—C(═O)—X, wherein X represents ahalogen atom); formyl group (—C(═O)—H); isocyano group; isocyanategroup; thiocyanate group or thioisocyanate group; provided that A¹ andA² may be cross-bridged with each other to form a ring shown by formula:—C(═O)—B—C(═O)— (wherein B is oxygen atom or a group shown by formula—N(B¹)— (wherein B¹ is hydrogen atom, a C₁-C₄₀ hydrocarbon group or ahalogen atom))), and, at least 5 of R¹, R², R³, R⁴, R^(5a), R^(5b), R⁶,R⁷, R^(8a), R^(8b), R⁹, R¹⁰, A¹ and A² are groups other than hydrogenatom.
 28. The process of producing the polyacene derivative according toclaim 27, wherein at least 6 of R¹, R², R³, R⁴, R^(5a), R^(5b), R⁶, R⁷,R^(8a), R^(8b), R⁹, R¹⁰, A¹ and A² are groups other than hydrogen atom.29. The process of producing the polyacene derivative according to claim27, wherein at least 7 of R¹, R², R³, R⁴, R^(5a), R^(5b), R⁶, R⁷,R^(8a), R^(8b), R⁹, R¹⁰, A¹ and A² are groups other than hydrogen atom.30. The process of producing the polyacene derivative according to claim27, wherein at least 8 of R¹, R², R³, R⁴, R^(5a), R^(5b), R⁶, R⁷,R^(8a), R^(8b), R⁹, R¹⁰, A¹ and A² are groups other than hydrogen atom.31. The process of producing the polyacene derivative according to claim27, wherein at least 9 of R¹, R², R³, R⁴, R^(5a), R^(5b), R⁶, R⁷,R^(8a), R^(8b), R⁹, R¹⁰, A¹ and A² are groups other than hydrogen atom.32. The process of producing the polyacene derivative according to claim27, wherein at least 10 of R¹, R², R³, R⁴, R^(5a), R^(5b), R⁶, R⁷,R^(8a), R^(8b), R⁹, R¹⁰, A¹ and A² are groups other than hydrogen atom.33. The process of producing the polyacene derivative according to anyone of claims 20 through 26, wherein any one of the combinations of R¹and R², R³ and R^(10 , R) ⁴ and R⁹, R⁵ and R⁸, R⁶ and R⁷, and A¹ and A²are the same substituents.
 34. The process of producing the polyacenederivative according to any one of claims 27 through 32, wherein any oneof the combinations of R¹ and R², R³ and R¹⁰, R⁴ and R⁹, R^(5a) andR^(8a), R^(5b), and R^(8b), R⁶ and R⁷, and A¹ and A² are the samesubstituents.
 35. The process of producing the polyacene derivativeaccording to any one of claims 20 through 26, wherein any one of R¹, R²,R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹ and R¹⁰ is a C₁-C₄₀ hydrocarbon group whichmay optionally be substituted, a C₁-C₄₀ alkoxy group which mayoptionally be substituted, or a C₆-C₄₀ aryloxy group which mayoptionally be substituted.
 36. The process of producing the polyacenederivative according to any one of claims 27 through 32, wherein any oneof R¹, R², R³, R⁴, R^(5a), R^(5b), R⁶, R⁷, R^(8a), R^(8b), R⁹ and R¹⁰ isa C₁-C₄₀ hydrocarbon group which may optionally be substituted, a C₁-C₄₀alkoxy group which may optionally be substituted, or a C₆-C₄₀ aryloxygroup which may optionally be substituted.
 37. The process of producingthe polyacene derivative according to any one of claims 20 through 24,wherein the case in which R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, A¹and A² are all hydrogen atoms in the formula (I) above, is excluded. 38.The process of producing the polyacene derivative according to any oneof claims 20 through 26, wherein n is 1; at least R¹, R², R⁴ and R⁹ aregroups other than hydrogen atom or at least R³, R⁵, R⁸ and R¹⁰ aregroups other than hydrogen atom and the cases of (a), (b), (c) and (d)are excluded: (a) when R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, A¹ andA² are all methyl groups; (b) when R³, R⁴, R⁹ and R¹⁰ are all arylgroups that may optionally be substituted; (c) when R¹, R², R⁴ and R⁹are all alkoxy or aryloxy groups, and R³, R⁵, R⁶, R⁷, R⁸, R¹⁰, A¹ and A²are all hydrogen atoms; (d) when R³, R⁵, R⁸ and R¹⁰ are all alkoxy oraryloxy groups, and R¹, R², R⁴, R⁶, R⁷, R⁹, A¹ and A² are all hydrogenatoms.
 39. The process of producing the polyacene derivative accordingto claim 27, wherein the polyacene derivative is the pentacenederivative represented by formula (Ia) above, and the cases of (a′),(b′), (c′) and (d′) below are excluded: (a′) a pentacene derivativerepresented by formula (Ia) below:

wherein R¹, R², R³, R⁴, R^(5a), R^(5b), R⁶, R⁷, R^(8a), R^(8b), R⁹, R¹⁰,A¹ and A² are all methyl groups; or R¹, R², R³, R⁴, R^(5a), R^(5b),R^(8a), R^(8b), R⁹ and R¹⁰ are all hydrogen atoms and at least one ofR⁶, R⁷, A¹ and A² is an aryl group; or at least one of R¹, R², R³, R⁴,R^(5a), R^(5b), R⁶, R⁷, R^(8a), R^(8b), R⁹, R¹⁰, A¹ and A² is adiarylamine group; (b′) a pentacene derivative represented by formula(Ib) below:

wherein R¹, R², R^(5b) and R^(8b) are all alkoxy or aryloxy groups; (c′)a pentacene derivative represented by formula (Ic) below:

wherein at least 2 of R³, R^(5a), R^(8a) and R¹⁰ are aryl or arylalkynylgroups; or at least one of R³, R^(5a), R^(8a) and R¹⁰ is an arylalkenylgroup; or R³, R^(5a), R^(8a) and R¹⁰ are all alkoxy or aryloxy groups;(d′) a pentacene derivative represented by formula (Id) below:

wherein R⁴ and R⁹ are hydrogen atom, a hydrocarbon group, an alkoxygroup, an aryloxy group, a halogen atom or hydroxy group.
 40. Theprocess of producing the polyacene derivative according to any one ofclaims 20 through 24, wherein when n is 1, A¹ and A² are analkoxycarbonyl group, and R¹, R², R⁴ and R⁹ are an alkyl or aryl group.41. The process of producing the polyacene derivative according to anyone of claims 20 through 24, wherein when n is 1, A¹, A², R¹, R², R⁴ andR⁹ are an alkyl or aryl group.
 42. The process of producing thepolyacene derivative according to any one of claims 20 through 24,wherein when n is 1, A¹ and A² are a halogen atom and R³, R⁵, R⁶, R⁷, R⁸and R¹⁰ are an alkyl or aryl group.
 43. The process of producing thepolyacene derivative according to claim 27, wherein when the polyacenederivative is the pentacene derivative represented by the formula (Ia)above, A¹ and A² are an alkoxycarbonyl group and R¹, R², R⁴, R^(5b), R⁶,R⁷, R^(8b) and R⁹ are an alkyl or aryl group.
 44. The process ofproducing the polyacene derivative according to claim 27, wherein whenthe polyacene derivative is the pentacene derivative represented by theformula (Ia) above, A¹, A², R¹, R², R⁴, R^(5b), R⁶, R⁷, R^(8b) and R⁹are an alkyl or aryl group.
 45. The process of producing the polyacenederivative according to claim 27, wherein when the polyacene derivativeis the pentacene derivative represented by the formula (Ia) above, A¹and A² are a halogen atom and R³, R^(5a), R^(8a) and R¹⁰ are an alkyl oraryl group.
 46. An electrically conductive material comprising thepolyacene derivative according to any one of claims 1 through 19 or thepolyacene derivative obtained by the process according to any one ofclaims 20 through
 45. 47. A resin composition comprising the polyacenederivative according to any one of claims 1 through 19 or the polyacenederivative obtained by the process according to any one of claims 20through 45, and other synthetic organic polymers.